High Pressure Crystallography: Status Artis and Emerging Opportunities

49th Course
High-pressure crystallography:
status artis and emerging opportunities
A NATO Advanced Study Institute
Erice, Italy 27 May -5 June 2016
Acknowledgements
This Nato Advanced Study Institute is supported through the Nato Science for
Peace and Security Programme.
It is also sponsored by:

OPCW
International Union of Crystallography
European Crystallographic Association
The Cambridge Crystallographic Data Centre (CCDC)
PANalytical
Bruker
Compress
Incoatec
Rigaku
Almax
Garland Science
Erice International School of Crystallography 49th Course, 27 May - 5 June 2016
Organisers
Course Directors
Francesca Fabbiani
John Parise
Malcolm Guthrie
Local Organisers
Paola Spadon
Annalisa Guerri
IT Support
Fred Boyle
Erin Davis
Organisers
Orange scarves
Chiara Anzolini
Paolo Lotti
Julia Magliozzo
Fabio Nicoli
Giovanna Scapin
Nicki Siersch
Andy Stewart
Programme
Saturday, 28 May 2016

8:40-9:00
Welcome and opening remarks
Guerri, Spadon, Davis, Fabbiani, Parise, Guthrie
9:00-9:45
Malcolm McMahon
High-pressure crystallography: an introduction
9:45-10:30
Ross Angel
Pressure and Equations of State
10:30-11:00 Coffee break
11:00-11:45

Jon Eggert
Dynamic compression: principles
11:45-12:30 Tetsuo Irifune

Multianvil techniques and their applications in Earth and
materials sciences
12:30-14:30
Lunch
14:30-15:15

Malcolm McMahon
Synchrotron X-ray diffraction techniques, and complex
structures of the elements
15.15-16:00 Malcolm Guthrie

Neutron diffraction
16:00-16:30
Coffee break
16:30-17:15
Workshops introduction
17:15-18:00
Workshops introduction + sign up
18:00-20:00 Free time

20:00
Welcome buffet & Folk show
Sunday, 29 May 2016

9:00-9:45
Ross J. Angel
High-pressure phase transitions
9:45-10:30
Simon Parsons
Understanding phase stability: intermolecular interactions in
molecular crystals
11:00-11:45 Sandro Scandolo

Theoretical aspects of materials properties at extreme p/T
conditions
11:45-12:30 Ross J. Angel
Principles of intensity data reduction
12:30-14:30
Lunch
14:30-15:15
Short (2-3 mins) presentations of poster (odd numbers)
15:15-16:00
Demo: Angel (EosFit)
16:00-16:30
Coffee break
16:30-18:00 Bruker - pure demo

EosFit - follow me
CCDC Workshop
HP cryst (10 students only)
18:00-20:00 Poster Session (odd numbers)
20:00
10
Pasta Party
Monday, 30 May 2016

9:00-9:45
Jon Eggert
Dynamic compression: applications
11:00-11:45

Sakura Pascarelli
An introduction to X-ray Absorption Spectroscopy
11:45-12:30

Livia E. Bove
Ices, salty ices and ice clathrates structures
12:30
EXCURSION 1
11
Tuesday, 31 May 2016

9:00-9:45
Helen Maynard-Casely
Synchrotron and neutron studies in planetary science
11:00-11:45

Sakura Pascarelli
Introduction to X-ray Magnetic Circular Dichroism
11:45-12:30

Nick Brooks
Biological systems and high-pressure SAXS
12:30-14:30
Lunch
14:30-16:00 ABSORB - demo

Clathrates - follow me
CCDC Workshop
16:00-16:30
Coffee break
16:30-18:00 EXAFS - follow me

PIXEL - hands-on
18:00-20:00 Free Time
12
Wednesday, 1 June 2016

9:00-9:45
Francesca P.A. Fabbiani
High-pressure crystallography of pharmaceutical drug molecules
9:45-10:30
Simon Parsons
Single molecule magnets
11:00-11:45

Karena W. Chapman
Pair distribution function analysis
11:45-12:30 Workshop: communication of high-pressure crystallography

(Maynard-Casely)
12:30-14:30
Lunch
14:30-15:15
Short (2-3 mins) presentations of poster (even numbers)
15:15-16:00
Bruker - pure demo
16:00-16:30
Coffee break
16:30-18:00 PDF - demo

EXAFS - follow me
PIXEL - hands-on
18:00-20:00 Poster Session (even numbers)
20:00
Pizza Party
13
Thursday, 2 June 2016

9:00-9:45
Denis Machon
Pressure-induced amorphisation
9:45-10:30
Andrzej Katrusiak
High-pressure crystallization
11:00-11:45 Roman Martok

Crystal structure prediction and metadynamics simulations at
high pressure
11:45-12:30

Chrystle Sanloup
Liquids and glasses at high pressure
12:30
EXCURSION 2 (buffet dinner at Segesta)
14
Friday, 3 June 2016

9:00-9:45
John B. Parise
Techniques for materials discovery and optimized HP synthesis
9:45-10:30

Selected participants talks
Davide Comboni
High pressure behaviour of AlPO4-5 in penetrating/ non
penetrating pressure medium
Piotr Guka

Crystal structure of cubic arsenic(III) oxide and its helium

clathrate under pressure

11:00-11:45

Karena W. Chapman
High pressure crystallography of metal-organic frameworks (MOFs)
11:45-12:30

Wendy Mao
New materials under extreme environments
12:30-14:30
Lunch
14:30-16:00

16:00-16:30
Coffee break
Lauren Connor

Crystal engineering of multicomponent constructs and the impact of
high pressure
Kirsten Schulze

Comparative HP/HT elasticity measurements on single-crystals

of hydrous/iron-bearing ringwoodite
Andrew Cairns

New mechanisms for negative linear compressibility in molecular
framework materials
Hannah Shelton

The evolution of interatomic and intermolecular interactions and

polymorphism of melamine at high pressure
16:30-18:00 EosFit - follow-me

Communication of HP crystallography
PDF - hands-on

18:00-20:00 Free Time
15
Saturday, 4 June 2016

9:00-9:45
Malcolm Guthrie
Instrumental innovations at neutron sources
9:45-10:30
Wendy Mao
Advances in instrumentation at photon sources
11:00-12:30 Selected participants talks

Xenia Ritter

Density of carbonate melts along the CaCO3-MgCO3 join by

synchrotron X-ray radiography

Christopher Woodall

The best of both worlds; combined X-ray and neutron studies at high
pressure using lab source X-ray diffractometers and laue neutron diffraction

Sulgiye Park

Effects of irradiation-induced structural disordering in zirconate

pyrochlores at high pressures

Dominique Laniel

Unexpected high pressure and high temperature chemistry in
Xe-N2 mixtures
12:30-14:30
Lunch
14:30-15:15

Christian Childs
Laser annealing after a kinetically hindered phase transition in the
pyrochlore La2Sn2O7: A method for true structure determination and a
pathway to recovery
Ramesh Devarapalli
Distinct mechanical response of brittle, plastic and elastic single crystals
studied by nanoindentation technique
15:15-16:00
Future challenges round table
16:00-16:30
Coffee break
16:30-17:15
Future challenges panel discussion
17:15-18:00
Closing remarks and Awards
18:00-20:00 Free time

20:00
16
Good Bye buffet dinner
Invited Speakers Contributions

(in chronological order of presentation)
17
18
High Pressure Crystallography An Introduction
High Pressure
crystallography An introduction
Malcolm
McMahon
mim@ph.ed.ac.uk
Malcolm McMahon
www.mimcmahon.com
School of Physics & Astronomy, The Univ. of Edinburgh, Edinburgh, UK

mim@ph.ed.ac.uk
www.mimcmahon.com
Abstract
In this introduction to high-pressure crystallography, I briefly review the history of the field, and
then describe the equipment and experimental methods used to determine the structures of
high-pressure phases using x-ray and neutron diffraction. Finally, I look to see what new
techniques may become prevalent in the upcoming decade.
Keywords
High-pressure, crystallography, x-ray-diffraction, neutron-diffraction
What is Crystallography?
The OED defines crystallography as That branch of physical science which treats of the structure
of crystals, and their systematic classification. In what follows, the determination of a structure
will mean the determination of the fractional coordinates of atoms, and their displacement
parameters, in a crystalline material. At high pressures, this typically involves the measurement
of the intensities of Bragg reflections using X-ray or neutron diffraction, followed by structural
solution and/or least-squares refinement.
A Brief History of High Pressure Crystallography
The history of high-pressure science is well described in two books by R.M. Hazen, and readers
are directed to these for an excellent introduction to the field1,2. High-pressure crystallography
started in the 1950s, using designs of pressure cell in which single-crystal diamonds were used in
a piston-cylinder arrangement, with a small cylindrical sample chamber being drilled through a
large diamond
The invention of the diamond anvil cell (DAC) in the late 1950s3,4 was the key turning point in
high-pressure crystallography, and diffraction studies were performed almost immediately
afterwards by its inventors, who determined the structure-types of various high-pressure phases
by matching observed X-ray diffraction patterns with those obtained from other materials at
ambient pressure5-8.
The development of the Merrill-Bassett DAC allowed DACs to be used on commercial
diffractometers9, and they were used extremely successfully in the 1970 and 1980 by researchers
at the Geophysical Laboratory at the Carnegie Institution of Washington to explore the
structures of complex minerals at high pressure, and to pioneer numerous high-pressure single-
19
crystal diffraction techniques, as described by Hazen and Finger10. This was real
crystallography, with the collection of large data sets, and the refinement of complex mineral
structures.
The high x-ray fluxes available from synchrotrons in the 1970s enabled diffraction studies to be
pushed to ever higher pressures: firstly 1 Mbar (100 GPa) in 197611, then 200 GPa in 198412, 300
GPa in 198913 and 400 GPa in 199014 (or perhaps in 201015). However, I would argue that many of
these diffraction studies were not crystallographic. They typically used energy-dispersive X-ray
powder-diffraction (EDXRD) methods in order to utilise the extreme intensity of the
polychromatic (white) synchrotron X-ray beam. As a result it was not possible to determine
accurate Bragg peak intensities and therefore refine structures. The crystallographic information
on many high-pressure phases remained at the level of structure type (cubic, tetragonal) or
distortions thereof. (See, for example, many of the phase diagrams reproduced in Ref. 16,
which is an excellent summary of our knowledge on the high-pressure behaviour of the elements
as of 1990).
Perhaps, the major transformation in high-pressure crystallography came about through, first,
the pioneering application of image-plate detectors for angle-dispersive X-ray powder diffraction
(ADXRD) in Japan in the late 1980s17, and their subsequent development at the SRS synchrotron
in the UK18,19. Within two or three years, it became fairly routine to perform crystallography to
extreme pressures comparable in quality to ambient-pressure studies.
ADXRD techniques allowed profile (Rietveld) refinement of high-pressure powder diffraction
data for the first time19,20, and two things became immediately apparent: (1) the structural
descriptions reported previously for many materials were incorrect16, and (2) the true structural
behaviour at high pressures was often extremely complex20.
These developments were perfectly timed with regards to the start-up of third generation
synchrotron sources (the ESRF, APS and SPring-8) in the mid-1990s. These machines were
ideally suited to ADXRD studies21, and allowed high-pressure crystallography to be pushed both
to ever higher pressures and to the most weakly-scattering systems22,23.
Simultaneously with these developments, chemical crystallography beamlines on synchrotrons2426
were being exploited to conduct high-pressure single-crystal studies, enabling ever more
complex systems to be studied, including proteins and biological systems27-29. Techniques were
developed to grow single crystal of phases that exist beyond strongly first-order phase
transitions, and these led to the almost immediate discovery of a host of incommensurate crystal
structures in a wide variety of elements, as reviewed in Ref. 30. The solution to these very
complex structures could almost certainly not have been determined from powder data alone,
and have been extended to well above 100 GPa31.
While the combination of DACs and synchrotrons have dominated high-pressure
crystallography since the 1970s, powder and single-crystal studies have continued to be
conducted at neutron sources around the world, exploiting the power of neutrons to probe H/D-
20
containing materials32,33, magnetism34,35 and phonons36, or to make high real-space resolution

studies of thermal motion37.
Such studies generally give very high quality diffraction data, and structural information that can
be superior to that obtainable by X-ray methods. But they are limited to low pressures,
constrained by the weakness of neutron sources, and the large samples (tens of cubic
millimetres) therefore required to obtain useable diffraction data.
However, the 1990s saw a revolution in high-pressure neutron science, with the advent of the
compact ParisEdinburgh (P-E) press in 199238 which enabled neutron powder-diffraction
structural studies to be pushed routinely to above 25 GPa39 while, more recently, full singlecrystal data collection with sufficient, and sufficiently-accurately measured, intensities for full
structure refinement has been extended to above 10 GPa40.
The P-E press can compress a sufficient volume of powder (or size of single crystal) to obtain
high-quality data, and is small enough to mount in situ on a neutron beamline. P-E presses have
opened high-pressure neutron diffraction to a much wider range of users, and have become a
standard experimental facility at several neutron sources. As a result, they have been used to
study a wide range of materials, both crystalline and amorphous41-45, and have also been widely
used at synchrotron sources for studies of non-crystalline materials and liquids, for example46-48.
Experimental Methods
The use and history of the DAC has been extensively reviewed by others, and the reader is
referred to these excellent reviews for detailed further information10,49-61.
Figure 1. Schematic diagram of a diamond anvil cell (DAC). The sample, pressure calibrant and hydrostatic fluid are
loaded into the gasket hole, which is then compressed between the culets of the two diamond anvils.
The basics of the DAC are shown in Fig. 1. Excellent descriptions of how to align and load a
DAC have been described by Miletich et al.51. The diamonds are gem-quality stones with a culet
size of 30600 m: the smaller the culet, the higher the achievable pressure. For pressures above
100 GPa, where the tip of the diamond undergoes significant distortion, bevelled diamonds are
used62. The anvils are mounted on seats, made of a hard X-ray transparent material such as Be or
BN, or tungsten carbide. The metallic gasket between the anvils is initially ~200 m thick, but is
21
pre-indented to 550 m before the sample chamber is drilled by spark erosion or laser drilling.
The diameter of the sample chamber is typically one-third of the diameter of the flat culet. The
sample is loaded into the gasket hole, and surrounded by a pressure transmitting fluid which
might be an alcohol:water mixture (which provides a quasi-hydrostatic medium to ~1016 GPa)
or a crystalline gas such as Ar, Ne or He (loaded either at high pressures or cryogenically as a
liquid) which is quasi-hydrostatic to 50 GPa or so63-66, or a soft solid. Along with the sample, it is
also necessary to include a pressure calibrant, which might be a small (5 m diameter) piece of
ruby or other fluorescing material, the fluorescence wavelength of which is known to change
with pressure, or a diffraction calibrant (e.g. Au, Cu, Ta) whose equation of state is known
For crystallographic studies, the incident X-ray beam typically enters the sample through one
anvil, and the diffracted X-rays exit through the other. In order to ensure that the maximum
amount of powder diffraction data are accessible, the opening angle in the anvil seat on the exit
side of the pressure cell should be as large as possible. Anvil seats with conical apertures with a
full opening angle of 4=70 are now used routinely.
For single-crystal studies, the opening angle on the incident-beam side of the DAC must be
equally large. Even so, in a DAC only a limited fraction of all single-crystal reflections are
accessible51,61. This restriction can have serious consequences for the refinement of certain
crystallographic parameters, and can be overcome by using a DAC with a transverse diffraction
geometry67, in which diffraction takes place in approximately the plane of the (typically X-ray
transparent) gasket. Using such cells, the volume of reciprocal space accessible in single-crystal
studies is increased considerably. However, the complex X-ray attenuation corrections required
with such cells mean that they are not as well suited to crystallography as those using the
transmission geometry.
DAC technology continues to develop. BoehlerAlmax (B-A) anvil seats68 mean that DACs no
longer need to use X-ray transparent seats in order to have the widest possible angular
apertures28. BA seats also enable cells with full conical apertures to be used at pressures to 150
GPa31. A still more recent development has been to use transparent anvils made from sintered
nanocrystalline diamond69-71.
The sample volumes required for neutron-diffraction means that standard DACs cannot be used
although successful attempts have been made to use DACs with extremely large anvils72. More
typical pressure cells for neutron diffraction typically fall into three different categories: (1) cells
utilising high-pressure gas to compress the sample, (2) those utilising a piston-cylinder
arrangement and (3) cells with opposed anvils. Gas cells73 can compress several cubic
centimetres of sample perfectly hydrostatically to 1 GPa by using He gas. Pistoncylinder
designs74,75, use a liquid pressure medium, and pressures of 2 GPa are achievable with both
powder and single-crystal samples. These cells are easily have also been designed to be inserted
into cryostats, extending studies to temperatures of 4 K and below.
The widest pressure range is achieved with opposed-anvil designs. By using very large diamonds,
Glaskov et al.72 were able to collect diffraction data from a single-crystal of D2 to 40 GPa,
22
although the diffraction information was limited to the d-spacings of one or two strong peaks. A
similar DAC was used to study single-crystals of D2 to 38 GPa at temperatures down to 1.2 K76.
And an opposed-anvil cell with moissonite anvils has been developed at the LANSCE neutron
source for use up to 20 GPa77,78. To increase the sample size, opposed-anvil cells for neutron
diffraction have used toroidal anvils in which toroidal grooves are cut into the anvils around the
sample volume79,80. This anvil design has been applied particularly successfully in both the Paris
Edinburgh38 and other78 presses.
The ParisEdinburgh press is shown in Fig. 2. The press can use a variety of anvil designs, with
the toroidal anvils79 being particularly popular. The PE cell can compress 100 mm3 to 10 GPa
and 35 mm3 to 30 GPa38,39. Samples can also be contained in encapsulated gaskets81,82, which
allow fluids or compressed gases to be user as pressure-transmitting media or samples83. A
smaller version of the cell has been designed for single-crystal diffraction studies84, and has been
used to collect and refine full single-crystal data sets to 10 GPa40. This cell can also be cooled to
35 K using a closed-cycle refrigerator
Crystallographic Techniques
There are four principal methods of determining crystal structures at high pressures using
powders or single-crystals, X-rays or neutrons. Here I give a brief review of the relevant
diffraction techniques and analysis methods used with each technique, focusing on recent
developments.
Figure 2. Schematic diagram of the VX3 model of the Paris-Edinburgh (P-E) press. Key: (1) Hardened steel main frame;
(2) Breech; (3) Piston; (4) Hydraulic fluid inlet; (5) Tungsten carbide toroidal-profile anvils with 2_ bevel angle; (6)
Sample chamber. Note the scale.
X-Ray Powder Diffraction

Only with the introduction of ADXRD on synchrotron sources in the 1990s did it become
routine to determine atomic positions using this technique at high pressure. While the majority
such studies have been performed at synchrotrons, laboratory-based studies have also been
performed85-88.
23
The use of powders greatly simplifies sample loading. And since many pressure-induced phase
transitions are strongly first order, samples which are loaded as single crystals do not typically
remain single crystals as the pressure is increased. Prior to 1990 powder-XRD studies typically
used energy-dispersive diffraction (EDX) techniques at synchrotrons, with polychromatic
radiation and an energy-resolving detector (see for example, ref. 89). Although the extremely
high intensity of the white synchrotron beam meant that diffraction data could be obtained at
pressures in excess of 300 GPa13, the poor energy resolution of the detector, and the very tight
collimation of both the incident and diffracted beams, meant that the diffraction patterns had
broad peaks, and poor powder averaging. Combined with the many -dependent corrections
that need to be applied to the data (e.g. sample and pressure cell absorption, synchrotron flux,
scattering power, detector efficiency), these limitations meant that accurate intensities were not
measurable, and crystallography wasnt possible. Structure determination thus remained at the
level of lattice type or structure type, e.g. tetragonal, -tin or distortions thereof. Distorted
typically meant that additional reflections were observed, but were not interpretable.
Figure 3. (a) 2D diffraction pattern collected from a polycrystalline sample Pr at a pressure of 19 GPa. The data were
collected in a 2s exposure on beamline ID09 at the ESRF synchrotron, during which the diamond anvil pressure cell was
oscillated 9 to improve the powder averaging. This large oscillation angle resulted in the appearance of a number of
Bragg reflections (marked with a D) from the anvils of the pressure cell. (b) The resulting 1D diffraction profile, after
azimuthal integration of the 2D pattern using Fit2D. The diamond reflections were omitted from the integration.
ADXRD techniques revolutionised high-pressure crystallography19. They used monochromatic

radiation, DACs with full conical apertures, and a highly-sensitive area detector to collect the 2D
Debye-Scherrer (D-S) pattern17,18; see Fig. 3a. These are then integrated azimuthally to provide a
standard 1D diffraction profile (Fig. 3b) which has high resolution, and, because of the
integration process, both accurate peak intensities and an extremely high signal-to-noise19,90,91.
The resulting increase in data quality is illustrated in Fig. 4, which shows ADX and EDX data
from the same sample. The combination of the high-resolution 2D data and the GUI software
made it possible to distinguish mixed phases simply from the difference in appearance of the
diffraction rings93,94. The 1D diffraction profiles are also ideally suited to profile (Rietveld)
refinement from which atomic coordinates can be obtained.
24
The collection of full 2D diffraction profiles revealed that samples which were very good
powders when loaded, giving smooth D-S rings, could sometimes recrystallise at high pressure,
giving very spotty diffraction patterns93. The later discovery that this phenomenon is relatively
widespread has enabled single-crystal studies beyond the first-order phase transitions that had
been thought to prohibit such studies.
X-Ray Single-Crystal Diffraction
The development of the small Merrill-Bassett DAC (MB-DAC) in 1974 meant that single-crystal
studies could be performed on standard single-crystal diffractometers9. As such studies require
the widest-possible access to reciprocal space, the anvils in an MB-DAC sit on x-ray transparent
Be anvil seats9 (Fig. 5a) . While Be seats provide the necessary angular access for both incident
and diffracted x-rays, the tensile strength of Be is quite low, particularly at high temperatures,
limiting the pressures available with such cells. BeO is also toxic, and the seats introduce an
additional angle-dependent absorption correction95 and a high background if the straight
through beam hits them96.
Figure 4. Diffraction profiles collected from the same powdered sample of InSb at ~2 GPa, using (top) energy- and
(bottom) angle-dispersive diffraction. The angle-dispersive data clearly have higher angular resolution, and are not
contaminated by X-ray fluorescence peaks. The tick marks below the angle-dispersive data mark the positions of some of
the weak superlattice reflections that were essential to determining the structure of the InSb-IV phase.
These problems have been solved completely by the use of so-called BoehlerAlmax anvil
seats68, in which the anvil has a double-conical shape, and fits into a conical aperture in the seat
(Fig. 5c). The result is a much stronger design in which wide-angle apertures can be obtained
from a seat made only of tungsten carbide28. Using such seats, it is possible to utilise wideangular openings to pressures above 150 GPa, giving high-quality single-crystal data at such
pressures31.
25
Figure 5. The different types of anvil seats used in DACs. In (a), the anvil sits on x-ray transparent beryllium, while in (b)
it sits on x-ray opaque tungsten carbide. The aperture in seat (b) is significantly larger than in (a) to allow the x-rays to
enter or exit the pressure cell over a sufficient angular range. The size of the aperture in (b) greatly reduces the support
to the base of the anvil. In (c), the anvil has a double-conical shape and is recessed into the tungsten-carbide seat. This
design allows a wide-angle aperture, while still strongly supporting the anvil. The anvil can also be reduced in size,
reducing cost.
The limited angular-access provided by all DACs means that data collection strategies need to be
optimised in order to ensure that all possible reflections are measured. Since 1990, a number
significant advances have resulted in single-crystal studies being extended to above 150 GPa. (1)
CCD detectors has revolutionised all crystallography by greatly speeding up data collection and
giving better quality data. Since samples in DACs are necessarily small, and the backgrounds
from DACs are high, then the increased signal-to-noise afforded by CCDs is universal in high-P
studies97,98. (2) In the mid-1990s, synchrotron beamlines furnished with CCD-equipped
diffractometers started to appear as user facilities. These offered a 1,000-fold intensity increase
over lab-based x-ray sources, and were perfectly suited to high-pressure studies25,26. (3) The
ability to survey all of the accessible reciprocal space on the CCD detector meant that all satellite
peaks and other features are collected automatically. Given the large number of high-pressure
studies that were later to show incommensurate phases, this ability has proved invaluable. (4)
The angular limitations imposed by DACs was overcome by using high-energy x-rays from
synchrotrons to compress reciprocal space.
All of these developments have been used in single-crystal crystallographic studies at
synchrotrons such as the ESRF, APS and SPring-8. Their short-wavelength can be focussed to
beams of only a few microns in diameter, meaning that studies can be performed using a beam
that is smaller than the sample crystal. This has enabled single-crystal studies to be performed
from samples within gasket holes only 15 m in diameter, with little, if any, diffraction from the
gasket97a,98a. The beamlines at such synchrotrons also lend themselves to the use of large
experimental apparatus, such as laser heating, resistive heating stages and cryostats. Singlecrystal studies are now thus possible over a very wide range of pressures and temperatures.
Neutron Powder Diffraction
The simplicity of neutron powder methods means that they have proved more popular than
single-crystal neutron studies. Diffraction data have been collected using both AD and ED
26
methods at reactor and pulsed (spallation) neutron sources, respectively. While detailed
crystallographic studies were conducted using neutron powder-diffraction methods prior to
1990, the upper pressure limited was 23 GPa. Parasitic neutron scattering from the pressure
cell can be greatly reduced on spallation neutron sources by collecting the diffraction data at 90
to the incident beam. With careful collimation of both incident and diffracted beams, only the
sample is both illuminated by the incident beam and viewed by the detector. The data can also
be corrected for pressure cell absorption and other systematic errors97b, resulting in accurate
relative peak intensities to very high scattering vectors on materials such as ammonia and gas
hydrates52,98b-100, liquid water101, and the various forms of high-pressure amorphous ice102,103.
In AD studies, an intense background can arise from the cell body, although the intensity of
these peaks can be greatly reduced by increased collimation of the detectors. When P-E cells are
employed on reactor sources, the use of highly-absorbing boron nitride anvils results in almost
all of the scattering from the anvils being absorbed, giving high quality diffraction profiles, ideally
suited to Rietveld refinement104.
Neutron Single-Crystal Diffraction
As with neutron powder methods, both AD and ED techniques have been used for single-crystal
neutron studies. Such studies are much less numerous, however, as a result of the difficulty of
compressing suitably-sized (>1 mm3) single-crystal samples.
Prompted by the success of the DAC, opposed-anvil cells equipped with large sapphire anvils
have been used in a number of high-resolution diffraction studies105-107 to perform high quality
studies to above 2 GPa. The quality of the data is excellent, particularly if collected using area
detectors108, the use of which is now widespread.
Large synthetic diamonds with a culet size of 3 mm109 have been used in a P-E press to
performed single-crystal studies to 3 GPa on a reactor source, and 17 GPa at a spallation source.
The large-anvil methods has been taken to its (current) extreme at SNS source, where B-A anvils
have been used to study samples to 94 GPa110,111.
Non-Ambient Temperature Studies
The strong links between high-pressure crystallography and mineralogy have meant that highpressure high-temperature (HPHT) studies have long dominated over low-temperature studies,
which are of more interest to physicists, for example see ref.112. While the great majority of
HPHT studies have employed powder methods, the methods employed are applicable to HP
HT single-crystal methods.
For DACs, heating comes in two distinctive forms, resistive and laser, with the former being
more convenient although the upper temperature is considerably less than that obtainable with
lasers. Two recent reviews113,114 provide an excellent introduction to HPHT methods.
In external resistive heating, the thermal conductivity of the cell body, diamonds and gasket are
used to transfer heat to the sample from a resistive heater placed around the cell body. In
internal resistive heating, a miniature heater is placed inside the DAC immediately around the
27
gasket and diamonds115,116. Resistively heated cells can attain >2,500 K117 if both internal and
external heaters are used.
Much higher temperatures can be achieved with laser heating, in which either ~1m or ~10 m
infrared radiation from Nd:YAG or CO2 lasers, respectively, is focused onto the sample. The
focus spots can be as small as ~10 m across, with temperature gradients of many 100 s of K per
micron. To ensure a uniformly-heated spot, the sample should be heated from both sides
simultaneously. For accurate crystallography it is essential that the x-ray beam be centred
precisely within the heated spot at all times, thereby ensuring that the diffraction data are
collected only from the heated region.
While it is difficult to maintain the alignment of the laser beam while the pressure cell is rotated
for single crystal studies, this has been done, and single-crystal data collected to megebar
pressures118,119. There has been a recent move to fibre lasers, the small size of which adds a
flexibility that is well suited to installation on synchrotron beamlines120. There are many papers
describing laser-heating systems, and the reader is pointed to these59,121-123, for more details of the
technique. Resistive heating has also been widely used in neutron diffraction studies, although
additional problems arise from the necessity of heating larger samples volumes for extended
periods of time. The P-E press has been used for neutron crystallographic studies to 10 GPa and
1,500 K82,124-127, while a P-E press, combined with a T-cup multi-anvil stage, has been developed
for AD x-ray diffraction studies to 25 GPa and 2,000 K128.
Low-T studies have typically been more popular in high-pressure neutron diffraction studies
than in x-ray studies, perhaps because of their combined use to study magnetism. All neutron
diffraction pressure cells can be cooled within cryostats. High-P low-T crystallographic studies
using x-rays have proved somewhat rarer, but are becoming more popular as cryostats appear as
standard sample environment equipment on some high-pressure synchrotron beamlines129,130.
21st Century Crystallography
After the revolutions of the 1990s, and the consolidation and exploitation of the last 15 years,
what does the future hold for high-pressure crystallography?
Pressures of 300 GPa were first generated in a DAC in 198913, but the maximum pressure of just
above 400 GPa attainable with traditional DAC designs had not, until 2012, increased
significantly in more than a decade. The key breakthrough in achieving pressures well above this
long-standing limit was made by Leonid Dubrovinsky and colleagues131. By utilising a
conventional DAC equipped with a second-stage set of micro-semi-ball anvils (10-50 m in
diameter) made of super-hard nano-crystalline diamond (see inset to Fig. 6), they extended the
upper pressure range of the DAC firstly to 640 GPa131 and, more recently, to above 1 TPa (10
Mbars) . The quality of the diffraction data obtained at these pressures using a 2 m diameter
synchrotron x-ray beam is remarkable, and this technical breakthrough is perfectly timed with
regards the availability of sub-micron diameter hard x-ray beams from upgraded 3rd generation
synchrotrons.
28
Figure 6. Schematic diagram of a two-stage DAC131, showing the secondary set of micro-anvils, between which the
sample is compressed (see enlargement). Note the different scales
As with previous eras in high-pressure science, new breakthroughs will arise through the
development of new X-ray and neutron sources. The high-pressure SNAP beamline at the new
spallation neutron source at Oak Ridge National Laboratory offers intensities much greater than
those currently available at the ISIS source, while new focusing technology will enable such
beams to be focused from a diameter of 1 cm down to <100 mm. This will enable single-crystal
studies of 1 mm3 samples to 50100 GPa on a routine basis110,111. At third generation
synchrotrons, facility upgrades to produce diffraction-limited output will enable x-ray beams to
be focused routinely to spot sizes below 1 m, allowing ever smaller samples to be studied to
ever higher pressures. The ESRF will close for its upgrade soon, with the APS a few years behind.
However, perhaps the biggest changes will come from the new x-ray free electron lasers in the
US (LCLS), Europe (European-XFEL) and Japan (SACLA). These laser-like X-ray sources
provide coherent radiation with peak brightnesses a billion times higher than existing storage
ring sources. The x-rays are also contained within ultra-short (50 fs) pulses, opening the way to a
host of experiments under extreme conditions131,132. The full possibilities of what such sources
will provide for static high-pressure diffraction experiments is not yet clear. Indeed, it is not yet
known whether the diamond anvils of a typical pressure cell will even survive being illuminated
by such ultra-bright x-ray pulses.
One area where such sources will offer great advantages is in using dynamic compression
techniques, where extremely intense laser beams with intensities of 1012 Wcm2 are used to
compress samples to extremely high densities over nanosecond timescales134. While relatively
little crystallography has been done to date using such techniques, this is changing, and recent
experiments have recorded X-ray diffraction data to above 1200 GPa135. In addition, advances in
laser compression science at the National Ignition Facility (NIF) in the US now provide the
possibility of compressing matter to multi-TPa pressures, such as those that exist at the centre of
Jupiter, in the near future. This is ten times the pressures currently accessible to static
compression techniques, and promises to reveal wholly new phases of matter. As always,
determining the crystal structure at these conditions will be crucial, and predicting the
structures of simple materials at these pressures has already produced some interesting results,
including a six-coordinated cubic host-guest phase of lithium136 and an incommensurate phase
29
of aluminium137. Studying the crystallography of matter at such conditions is no longer beyond

the realms of imagination, and promises many new discoveries over the coming decade.
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38
Pressure and Equations of State
Pressure
andDipartimento
Equations of
Ross
J. Angel,
diState
Geoscienze, Universit di Padova, Via G. Gradenigo 6, Padova,
35131, Italy.
Ross J. Angel
email: rossjohnangel@gmail.com
Dept Geosciences, Univ. of Padua, Padua, Italy

rossjohnangel@gmail.com
www.rossangel.net
Abstract
Equations of state (EoS) describe how the volume or density of a material varies with changes in
hydrostatic pressure and temperature within the elastic regime. Permanent change to a sample,
by plastic deformation or by brittle failure, or the application of non-hydrostatic stress
invalidates the assumptions behind the derivation of EoS. The origin of EoS in linear elasticity
theory is presented, and examples of the types of assumptions that allow various isothermal EoS
to be derived are discussed. The concept of thermal pressure is introduced to allow EoS to be
used for variations in temperature and pressure, and some guidelines for determining EoS
parameters from diffraction data are given.
Keywords
Pressure, Volume, Bulk Modulus, Elasticity, Equations of State

Introduction
pressure and temperature. Equations of state therefore provide fundamental thermodynamic
data that is required, for example, for the calculation of equilibrium phase diagrams1, 2. Equations
of state also define how some of the elastic properties of the material change in response to
compression and expansion. Because it is the interatomic interactions that resist the externallyapplied compressive stresses, knowledge of elastic properties provides insight into how
interatomic interactions change with decreasing distance3, 4, 5.
The fundamental measure of the response of a crystal structure to the application of hydrostatic
pressure at constant temperature is its isothermal bulk modulus, K = V (P V )T which is a
function of both temperature and pressure. The bulk moduli at ambient conditions of most
organic and metal-organic materials fall in the range of ~5 to 50 GPa, and for inorganic solids
range from ~25 to 400 GPa. They can be determined either by measuring the volume variation
of the material with pressure, usually by diffraction, or by direct measurement of the elastic
properties. Here I review the basics of linear elasticity and show how the bulk modulus is related
to the anisotropic elastic properties of a material, and then show how the change in the bulk
modulus with pressure can be modelled with isothermal EoS. Extensions to P-V-T EoS are
briefly discussed, and some guidelines are given for critically evaluating P-V and P-V-T data and
fitting them to obtain meaningful EoS parameters.
39
Relationship of EoS to Linear Elasticity

Equations of state are restricted to describing elastic behaviour. Elastic means that the changes
in the material are completely reversible when the pressure is removed. If there is permanent
change to the sample, the changes cannot be described by an EoS. Conventional linear elasticity,
as commonly met with metal springs, is defined by Hookes law. The extension of the spring is
proportional to the force applied to the spring. Springs are one-dimensional, so their response to
an applied force F can be written as
F = kl0 , in which l0 is the original length of the spring, k
is the spring constant representing its stiffness, and is the fractional change in length induced
by the force. If we associate a cross-sectional area A with the spring, then the applied stress is
kl0
, or
A
= F A and Hookes law can be re-written as the stress-strain relationship =

simply
= c with c being the elastic modulus or stiffness of the spring. We can also use the
1
softness or elastic compliance of the spring s = c so that we can write the equation that gives
the strain as a result of the applied stress: = s .
All crystals are anisotropic in their elastic properties, even cubic crystals. Extension of the
concept of linear elasticity to three dimensions therefore requires that the anisotropy of stress,
strain, and the elastic properties of the crystal are described in three dimensions. This requires
the use of tensors. Full details of the tensor approach to crystal physics can be found in the
classic text book by Nye6. For our purposes it is sufficient to express Hookes law as a matrix
equation in 3 dimensions, using the Voigt notation6:
1 s11

2 s 21
s
3 = 31
4 s 41
s
5 51
s
6 61
s12
s 22
s32
s 42
s52
s 62
s13
s 23
s 33
s 43
s 53
s 63
s14
s 24
s34
s 44
s54
s 64
s15
s 25
s 35
s 45
s 55
s 65
s16 1

s 26 2
s36 3

s 46 4
s56 5
s 66 6
(1)
The suffixes run from 1 to 6, with suffixes 1,2,3 referring to normal stresses or strains along
orthogonal axes, and suffixes 4,5,6 referring to shear stresses or strains6, 7. The elastic properties
of the material are represented by the values of the elements of the compliance matrix sij which is
symmetric and can contain up to 21 independent elements for triclinic crystals, less for crystals
and materials with higher symmetries. Equation (1) therefore allows the strains i to be
determined for any set of simultaneously applied stresses j. The normal convention is that
extensive stresses and strains are given positive signs.
Hydrostatic pressure is a special stress state in which the normal stresses are all equal
( 1 =
2 =
3 =
P ) and there are no shear stresses ( 4 = 5 = 6 = 0) . Thus, at any
pressure P, the strains caused by an infinitesimal increase in pressure P can be calculated
40
through linear elasticity theory by setting
1 = 2 = 3 = P . Note the signs here, because
while pressure is considered to be a positive quantity, compressive stresses are by convention

negative. Therefore each of the resulting strain elements is given by:
(2)
= (s + s + s ) = (s + s + s )P
i
i1
i2
i3
i1
i2
i3
The sum of the three normal strains is, in the infinitesimal limit, equal to the fractional change in
the volume
V V , thus:
( 1 + 2 + 3 ) = [s11 + s22 + s33 + 2(s12 + s13 + s23 )]P

V V =
(3)
Re-arrangement of this last equation shows that the bulk modulus for hydrostatic compression
at any pressure is defined by six of the elements of the compressibility matrix at that same
pressure:
1
(4)
K =
VP V =
s + s + s + 2(s + s + s )
[ 11
22
33
12
13
23
This bulk modulus for hydrostatic compression of a solid, whether a powder or single crystal, is
called the Reuss bulk modulus. It is also equal to the bulk modulus of a polycrystal made of the
same material provided every constituent grain is subject to the same stress.
Other bulk moduli, that do not apply to isothermal hydrostatic pressure conditions, can also be
defined in terms of the single-crystal elasticity. For example, the matrix equation (1) can be
written in short-hand as i
= sij j . The equation can be inverted to obtain i = cij j where
cij = sij1 is the modulus matrix and the inverse of the compliance matrix. If one now considers a
situation of uniform strain rather than uniform stress, one can obtain the Voigt bulk modulus:
(5)
K = (c + c + c + 2(c + c + c )) 9
V
11
22
33
12
13
23
The Reuss and Voigt bulk moduli are only identical for cubic crystals and isotropic materials, but
the difference between them does not necessarily increase with a decrease in symmetry. The
difference in values instead reflects the elastic anisotropy of the material. In triclinic albite
feldspar the difference between KR and KV is 20%8 but is more than 30% in portlandite9.
Adiabatic moduli
When a material is compressed as a result of an applied stress, work is done on the system and, if
the system is not allowed to dissipate this energy, it will heat up. In experimental methods such
as static compression or mechanical analysis that employ relatively long time scales compared to
atomic scale processes, this heat escapes to the environment and the experimental sample
remains at constant temperature throughout the measurement. The elastic properties obtained
from such experiments are termed isothermal, and they are given by equations 1-5. By contrast,
experimental probes such as spectroscopy are fast relative to the time required to dissipate heat
41
from a sample. As a consequence, the sample heats up as a result of the imposed stresses and the
strains include the effect of the thermal expansion in addition to those arising from the stress
alone. The values obtained for the elastic properties therefore differ from those measured
isothermally. When the system remains completely thermally isolated and the strains are
reversible (i.e. elastic), the system is said to be adiabatic, and the entropy of the system remains
P
.The difference between the values
V S
S
of the individual components of the adiabatic compliance matrix s ij and the isothermal matrix
constant. The adiabatic bulk modulus is K =

V
S
s ijT for values of only i,j = 1,2,3 is:

sijT sijS +
=
i j T
(6)
Cp
with Cp being the isobaric heat capacity of the crystal in units of Jm-3K-1. Summation over all
nine components of this equation with i,j = 1,2,3 gives the relationship between the isothermal
and adiabatic Reuss bulk moduli:
1
1 V2 T
=
+
Cp
KT K S
(7)
where V is the volume thermal expansion coefficient. The most commonly-used expression of
this relationship employs the thermodynamic Gruneisen parameter
that
V K S V KT
=
=
, so
Cp
CV
=
K S (1 + V T )K T . For inorganic solids the value of is about 1 at room conditions, so
KS is bigger than KT by about 1%. The difference increases considerably at higher temperatures10,
so adiabatic and isothermal values should not be compared without conversion. There is no
general theory that defines how varies with pressure and temperature, and different
approximations may be appropriate for different P and T ranges10.
Isothermal Equations of State
The isothermal Reuss bulk modulus (equation 4) defines how the volume of a material changes
after a small change in isotropic stress, that is a change in hydrostatic pressure. An equation of
state is therefore an extension of linear elasticity; although normally defined in terms of the
volume variation with pressure, it is also a definition of the variation of bulk modulus with
pressure. However, as solids are compressed the reduction in the inter-atomic distances leads to
an increase in bulk modulus (Fig. 1).
42
Figure. 1. Solid lines show the typical trends in volume and bulk modulus with pressure for a solid material. The dashed
lines show the variation for linear elasticity
There is no absolute thermodynamic basis for specifying how the bulk modulus varies with
pressure. For materials that do not exhibit phase transitions, isothermal equations of state are
therefore parameterized in terms of the values of the bulk modulus and its pressure derivatives,
K = K P and K = 2 K P 2 , at a reference pressure, normally zero pressure. These

values are denoted with a subscript 0, thus K0. All EoS that have been developed and are in
widespread use are based upon a number of assumptions10, 11, 12. The validity of such assumptions
can only be judged in terms of whether the derived EoS reproduces experimental data for
volume or elasticity. Here we take three examples to illustrate different ways in which EoS can be
developed. Further examples can be found in the literature10, 11, 12, 13.
Murnaghan EoS
One approach to deriving an EoS is to make an assumption about the way in which the bulk
modulus changes with pressure, or with volume. As an example, the Murnaghan EoS14 can be
derived from the assumption that the bulk modulus varies linearly with pressure, so
P
K P K 0 + K 0 P . Thus V= K 0 + K P which can be re-arranged:
=
V
P
V
P
V
=
0 K 0 + K P Vo V
(8)
Integration leads to the Murnaghan EoS which can be expressed as:

1
K P K
V V0 1 +
=
K
0
K 0 V0
P=
1
K V
(9)
(10)
The Murnaghan EoS has the advantage it is simple and can be expressed either as a function of V
or as a function of P. It also illustrates two basic principles that also apply to all EoS, and that
43
have implications for the way in which parameters are determined by fitting to P-V data. First,
the pressure term, for example in equation (9), is always scaled by the room-pressure bulk
modulus K0. Second, the volume only appears as a ratio to the room-pressure volume V0.
The disadvantage of the Murnaghan EoS is that K = K P = 0 , which is not true for
most solids. Hence the Murnaghan EoS cannot fit volume compression curves to more than 10%
compression and, further, fits of the Murnaghan EoS to P-V data often results in values of K0 that
do not agree with elasticity measurements. The Tait EoS1, 15 is an extension of the Murnaghan
2
EoS that allows

used.
K to be non-zero, and other EoS can be derived in similar ways16 but are less
Finite strain EoS

In the Murnaghan EoS the volume appears as a simple ratio to the room-pressure volume
(V0 V ) which is the definition of the volume strain used in linear elasticity. An alternative
approach to deriving an EoS is to assume that the strain energy of the material can be expressed
as a polynomial function of the strain. Different EoS are derived from different definitions of the
strain. As an example, the widely-used and successful Birch-Murnaghan17 EoS uses the the finite
Eulerian definition of strain, f E = (V0 V )

2
2/3
1 / 2 . The strain energy is then written as a
= af + bf + cf + ..... Different orders of the EoS are derived

polynomial in this strain as:
by truncating this polynomial at various terms. The simplest EoS is the 2nd-order form based on
=
af 2 . Derivation of the EoS now proceeds by taking the derivative of the energy with
respect to the strain to obtain the pressure:
P=
d df
d
=
dV
df dV
(11)
And a second derivative to obtain an expression for the bulk modulus, both of which include the
unknown parameter a from the original polynomial for the energy:
=
P
1
(1 + 2 f )5 / 2 [2af ]
3V0
P 2a
(1 + 2 f )5 / 2 [1 + 7 f ]
K==
V
V 9V0
(12)
One now uses the boundary conditions that at P=0, f=0 and K=K0 to obtain an expression for the
parameter a. Back-substitution then provides the 2nd-order Birch-Murnaghan EoS expressed for
both pressure and bulk modulus:
K0 =
2a
9V0
=
K K 0 (1 + 2 f )
5/ 2
=
P 3K 0 (1 + 2 f )
(1 + 7 f )
5/ 2
44
(13)
A similar but more painful process can be carried out to derive the 3rd and 4th-order BirchMurnaghan EoS based on the 3rd and 4th -order truncations of the polynomial of free energy in
the strains. The complexity of the expressions means that several published versions of the EoS
are incorrect, either through derivation errors, or simple typographical errors13.
Another family of EoS18, 19 has been developed in an analagous way, but based on the natural or
Hencky definition of linear strain
f N = 1 3 ln(V0 V ) .
f N which, for hydrostatic compression, may be written as
Using inter-atomic potentials.
The finite-strain EoS do not accurately represent the volume variation of most solids under very
high compression
(VPT
V0T < 0.6) . A natural solution would appear to be to define how inter-
atomic forces vary with inter-atomic distances, from which one can define how the internal
energy of the material varies with these distances. Given some geometric information about the
crystal structure, this can be turned into an expression of the energy dependence on volume.
The volume derivative of the energy then represents the pressure, and an EoS is obtained. A
large number of such EoS have been derived10, but most are for single types of atom-atom
interactions and built on central-force models, neither of which are appropriate for application
to complex materials.
P-V-T Equations of State
Pressure-volume EoS are well-developed and are capable of reproducing the isothermal volume
or density changes of materials to within the experimental uncertainties. A natural approach to
describing the P-V-T behaviour of a material is therefore to describe how the volume, bulk
moduli and its pressure derivatives change with increasing temperature (at room pressure), and
then use these parameters to calculate the isothermal compression at the temperature of interest
(Fig. 2). A potential limitation of this approach is that while the variation of KT with T can be
determined from elasticity measurements of KS, the variation of
K 0 with temperature has rarely
been measured, although it is obvious that it should increase slightly with increasing
temperature. A common assumption is that
K 0 does not change with temperature, and that
K 0T T is constant. However, this often leads to the prediction of non-physical negative

thermal expansion coefficients at reasonably modest pressures for a large number of materials20
and better parameterisations should be employed to avoid this problem.
45
Figure 2. Two paths to calculate P-V-T properties. The red path uses isobaric heating followed by an isothermal EoS.
The path of a thermal pressure calculation is shown by the blue arrows.
The alternative approach is to use the concept of thermal pressure10. The total pressure at a
given V and T can be expressed as the sum of two terms P (V , T ) = P V , Tref + Pth (T ) . The
) is the isothermal equation of state for the material at the reference

temperature, up to the volume at P and T. If T > T , then P (V , T ) <P (V , T ) as shown in
first term P V , Tref
ref
ref
Figure 2. The thermal-pressure Pth (T ) is the pressure that would be created by increasing the
temperature from Tref to T at constant volume, which is the isochor of the material passing
through the final P,T point of interest. As shown in the figure, the concept of thermal pressure is
therefore essentially a way of calculating P(V,T) along a different path in P-T space.
We can consider that the isothermal compression part that gives us P V , Tref
) is well-defined.
P
= K T , so the thermal pressure is therefore
T V
The slope of the isochor is given by
Pth =
(K )
T V
dT . In order to use a thermal-pressure EoS one then has to know, or to make
Tref
an assumption, about how the product K T varies along the isochor. For many materials and
P,T ranges of interest (e.g. Figure 2) the temperatures of interest are in the region of the Debye
temperature, so the isochor is linear and thus
KT is a constant. In this case
Pth ~ (K T )V (T Tref ) . A number of other assumptions or models of the behaviour of
materials can be made, including the Debye and similar models which make assumptions about
the vibrational and hence thermal behaviour of materials10. It should be emphasised that, despite
claims often made that the thermal pressure approach is somehow more fundamental than using
46
isothermal EoS at elevated temperatures, Figure 2 shows that they differ simply in the path in
P,T space used to calculate P(V,T). Both approaches require some assumptions about how EoS
parameters change with P and T, both of which can lead to unphysical behaviour. In the absence
of any measurements of isochoric measurements of K T one can argue that the 'isothermal
approach' is better because at least we have some direct measurements of the parameters
required.
Determining Equation of State Parameters
The parameters of an EoS can be measured by a variety of experimental techniques7, which can
be divided into two broad categories: those that measure the pressure-volume relationship, and
those that measure the elasticity directly. It is important to note that the latter are often not
really direct measurements of the elastic moduli. Ultrasonic interferometry, Brillouin scattering
and similar techniques actually provide measurements of elastic wave velocities. The general
relation between wave velocities v and elastic moduli is c = v , so it is necessary to obtain a
measurement of the density at the measurement conditions in order to obtain the values of the
moduli. For in-situ high-pressure elasticity measurements the density can be determined by
simultaneous diffraction measurement21, or the elastic moduli themselves can be used to define
the EoS in an iterative procedure to fit the data22.
The determination of meaningful EoS parameters from P-V data requires care for a number of
2
reasons. First, the parameters of interest such as K0 and
K 0 are derivatives of the data. This
makes the resulting values very sensitive to data precision and accuracy, and to the presence of
individual outlier data. In principle, collecting data over a wider pressure range should lead to
more precise EoS parameters, but many pressure media become non-hydrostatic above quite
modest pressures23 applying non-isotropic stress to the crystal. This invalidates the fundamental
assumptions behind EoS theory, besides changing the actual measured P-V curve. Sometimes
non-hydrostatic conditions are detectable by the broadening of the diffraction maxima. The
deviation in the P-V curve caused by non-hydrostatic stress is often subtle, but an algebraic rearrangement of the Birch-Murnaghan EoS provides a sensitive graphical tool to detect problems
in P-V data. The 4th-order Birch-Murnaghan EoS can be re-arranged by defining a normalised
pressure F =
P
, making the equation a polynomial in the finite strain24:
5/2
3 f E (1 + 2 f E )
3
3
35
=
F K 0T 1 + (K 0T 4 ) f E + K 0T K 0T + (K 0T 4)(K 0T 3) + f E2
2
9
2
(14)
If the data are represented by a 2nd-order EoS, then a plot of F against f will be a horizontal
straight line. A 3rdorder EoS will result in an inclined straight line, and a 4th order EoS in a
parabolic curve25. Non-hydrostatic conditions are often detectable by a deviation in the f-F plot,
for example as shown by the open symbols in Figure 3.
47
Figure 3. An f-F plot of two datasets of different materials, using Birch-Murnaghan definitions of finite strain and
normalized stress. The black symbols are data for quartz, a soft material26. The data lie on an inclined straight line
indicating that a 3rd-order EoS is required to describe the data. The open symbols are from a measurement of a stiffer
material to 28 GPa. The kink in the f-F plot corresponds to the freezing of the alcohol pressure medium.
Complete details about appropriate fitting procedures and diagnostics are provided in previous
reviews25. One of the most important points is a consequence of all EoS being scaled by the room
pressure volume and bulk modulus. While these values might have been measured, they are
subject to experimental uncertainties. If they have not been measured in the same experiment,
taking the values from another source may bias the entire fit of the data. Therefore, the values of
V0 and K0 must always be refined in a fit of P-V data. Individual data may be collected with
different uncertainties in either P, T or V; especially measurements made at room pressure have
considerably less uncertainty in pressure than the most accurate high-pressure determination. In
fitting EoS to P-V data it is therefore appropriate to use least-squares minimization weighted by
the estimated uncertainties in P, T and V, and this is the only way in which it is possible to make
an estimate of the reliability of the final refined parameters. The form of the EoS equations and
the limited data ranges mean that the final refined parameters obtained from fitting P-V data
alone are strongly correlated. This covariance must be considered when comparing the
parameter values such as K0 with those from other measurements. The EosFit suite of
programs13 provides the tools to evaluate and fit P-V-T data and can be downloaded from
www.rossangel.net.
Acknowledgments
This manuscript was prepared with the support of ERC starting grant 307322 to Fabrizio Nestola
of the University of Padova.
48
References
Holland TJB, Powell R. An improved and extended internally consistent thermodynamic dataset for phases
of petrological interest, involving a new equation of state for solids. Journal of Metamorphic Geology 29,
333-383 (2011).
Stixrude L, Lithgow-Bertelloni C. Thermodynamics of mantle minerals - I. Physical properties. Geophysical
Journal International 162, 610-632 (2005).
Brown I, Klages P, Skowron A. Influence of pressure on the lengths of chemical bonds. Acta
Crystallographica B 59, 439-448 (2003).
Zhao J, Ross NL, Angel RJ. New view of the high-pressure behaviour of GdFeO3-type perovskites. Acta
Crystallographica B 60, 263-271 (2004).
Fabbiani F, Pulham C. High-pressure studies of pharmaceutical compounds and energetic materials.

Chemical Society Reviews 35, 932-942 (2006).
Nye JF. Physical properties of crystals. Oxford University Press (1957).

Angel RJ, Jackson JM, Reichmann HJ, Speziale S. Elasticity measurements on minerals: a review. European
Journal of Mineralogy 21, 525-550 (2009).
Brown JM, Abramson EH, Angel RJ. Triclinic elastic constants for low albite. Physics and Chemistry of
Minerals 33, 256-265 (2006).
Speziale S, Reichmann H, Schilling F, Wenk H, Monreiro P. Determination of the elastic constants of

portlandite by Brillouin spectroscopy. Cement and Concrete Research 38, 1148-1153 (2008).
Anderson OL. Equations of State of Solids for Geophysics and Ceramic Science (1995).
Duffy TS, Wang YB. Pressure-volume-temperature equations of state. In: Ultrahigh-Pressure Mineralogy:
Physics and Chemistry of the Earth's Deep Interior (ed^(eds Hemley R). Mineralogical Society of America
(1998).
Holzapfel WB. Equations of state for solids under strong compression. Zeitschrift fr Kristallographie 216,
473-488 (2001).
Angel RJ, Gonzalez-Platas J, Alvaro M. EosFit7c and a Fortran module (library) for equation of state
calculations. Zeitschrift fr Kristallographie 229, 405-419 (2014).
Murnaghan F. Finite deformations of an elastic solid. American Journal of Mathematics 49, 235-260 (1937).
Huang YK, Chow CY. The generalised compressibility equation of Tait for dense matter. Journal of Physics
D: Applied Physics 7, 2021-2023 (1974).
Freund J, Ingalls R. Inverted isothermal equations of state and determination of B0, B'0 and B''0. Journal of
Physics & Chemistry of Solids 50, 263-268 (1989).
Birch F. Finite elastic strain of cubic crystals. Physical Review 71, 809-824 (1947).
Maier BJ, et al. Effect of La doping on the ferroic order in Pb-based perovskite-type relaxor ferroelectrics.
Physical Review B 83, (2011).
Poirier J-P, Tarantola A. A logarithmic equation of state. Physics of Earth and Planetary Interiors 109, 1-8
(1998).
Hellfrich G, Connolly JAD. Physical contradictions and remedies using simple polythermal equations of
state. American Mineralogist 94, 1616-1619 (2009).
Trots DM, et al. The Sm:YAG primary fluorescence pressure scale. Journal of Geophysical Research-Solid
Earth 118, 5805-5813 (2013).
49
Zouboulis I, Jiang F, Wang J, Duffy T. Single-crystal elastic constants of magnesium difluoride (MgF2) to 7.4
GPa. Journal of the Physics and Chemistry of Solids 75, 136141 (2014).
Angel RJ, Bujak M, Zhao J, Gatta GD, Jacobsen SD. Effective hydrostatic limits of pressure media for highpressure crystallographic studies. Journal of Applied Crystallography 40, 26-32 (2007).
Stacey FD, Brennan BJ, Irvine RD. Finite strain theories and comparisons with seismological data.
Geophysical Surveys 4, 189-232 (1981).
Angel RJ. Equations of state. In: High-pressure and high-temperature crystal chemistry (eds Hazen RM,
Downs RT). Mineralogical Society of America, Reviews in Mineralogy and Geochemistry v41 (2000).
Angel RJ, Allan DR, Miletich R, Finger LW. The use of quartz as an internal pressure standard in highpressure crystallography. Journal of Applied Crystallography 30, 461-466 (1997).
50
Multianvil techniques and their applications in Earth and materials sciences
Multianvil
techniques
andResearch
their applications
in University,
Earth andand Earth-Life Science
Tetsuo
Irifune,
Geodynamics
Center, Ehime
materials
sciences
Institute
(ELSI),
Tokyo Institute of Technology
email: irifune@dpc.ehime-u.ac.jp
Tetsuo Irifune
homepage:
Geodynamicshttp://www.grc.ehime-u.ac.jp/en/
Research Center, Ehime Univ., Earth-Life Science Inst. (ELSI), Inst. of
Technology, Tokyo, Japan
irifune@dpc.ehime-u.ac.jp
www.grc.ehime-u.ac.jp/en/
Abstract
Kawai-type multianvil apparatus (KMA) has been used for mineral physics studies, such as
accurate determinations of phase relations and measurements of physical properties of minerals,
at pressures to 30 GPa and temperatures up to 3000K, utilizing its great advantage in larger
sample volumes relative to those available in competitive laser-heated diamond anvil cell.
Moreover, the pressures achievable in KMA have been expanded by replacing the conventional
tungsten carbide anvils with those made of much harder sintered diamond, yielding pressures as
high as 100 GPa. The KMA technology is also important for synthesis of novel functional
materials, such as superhard materials and transparent ceramics, under ultra-high pressure
conditions.
Keywords
multianvil apparatus, mineral physics, materials synthesis, nano-polycrystalline diamond,

transparent ceramics
1. Introduction
Since the pioneering work of P. W. Bridgman and his co-workers in early 20th century, various
static high-pressure apparatus operated in a large-volume press have been invented and used for
studies in physics, geoscience, chemistry, and materials science under very high pressure. For
materials synthesis under the pressures lower than those in the ultrha-high pressure regime
(>10 GPa), either piston-cylinder and its modified version of belt (or girdle)-type apparatus or
cubic press, where relatively large sample volumes (~104-106 mm3, Fig.1a) 1 are available, have
been frequently used. In contrast, although diamond anvil cell is now capable of producing
pressures as high as 400 GPa, its use as a tool for materials synthesis is very limited because the
sample volume in this apparatus is extremely small (~<10-4 mm3).
Kawai-type multianvil apparatus (KMA or MA6-8) uses 6 first-stage and 8 second-stage anvils
(Fig.1b), which are compressed in a large-volume press with a hydraulic ram2. A conventional
KMA operated in a press with normally about 1000 ton ram capacity yields pressures to 30 GPa
in sample volumes of ~1-10 mm3, which fills the gap in the pressure-volume range available in
the above two types of high-pressure apparatus (Fig.1a). By using much harder sintered diamond
(SD) composite with some metal binders, pressures approaching 100 GPa are produced in some
laboratories3,4, although the sample volumes are limited to ~10-1-10-2 mm3. In contrast, by using a
51
KMA operated in a very large press (VLP, e.g. BOTCHAN-6000 with a 6000-ton press), larger
sample volumes of ~103 mm3 at pressures greater than 20 GPa are now available in our
laboratory at the Geodynamics Research Center (GRC)1. The KMA has been successfully used
for novel materials synthesis under the ultra-high pressure regime, which is inaccessible by
conventional belt-type apparatus or cubic press.
Figure 1. Pressures and sample volumes covered in various high-pressure apparatus (a) and a conceptual illustration of
Kawai-type Multianvil Apparatus, KMA (b). VLP = Very Large Press; SD = Sintered Diamond anvils; DAC = Diamond
Anvil Cell. Typical linear dimensions of the sample volumes are shown for a guide (a).
2. Guide blocks and anvils for KMA
The cell assembly placed in the second-stage cubic anvils of KMA is compressed in a hydraulic
press via a pair of guide blocks, where the first-stage hardened steel anvils are embedded5. There
are basically two types of guide blocks to pressurize the second-stage anvils; one is those with
split sphere (or split cylinder/Walker-type) first-stage anvils fixed in the cavities of the upper and
lower guide-blocks (Fig.2a), while another is so called DIA-type guide blocks, where four
sliding blocks equipped with the first-stage anvils move inward as the upper and lower guide
blocks approach each other upon compression (Fig.2b).
Figure 2. Split sphere-type (a) and DIA-type (b) guide blocks for operation of KMA.
Guide blocks with split sphere (split cylinder) first-stage anvils are structurally simpler and easier
in operation/maintenance compared to DIA-type guide blocks, and have been used in many
high-pressure laboratories, particularly for synthesis experiments using quench method. In
52
contrast, geometry of the latter guide blocks easily allows in situ X-ray observations, and most of
the large-volume apparatus installed at the beamlines in synchrotron facilities have this type of
guide blocks. Moreover, alignments of the first-stage anvils in DIA-type guide blocks are easily
adjusted so that the second-stage anvils can be evenly compressed. This is particularly important
in pressurizing a small cell assembly with the second-stage anvils of sintered diamond, where the
size of the anvil is very limited (generally 10-14 mm in edge length of an anvil).
Eight tungsten carbide (WC) cubes are used as the second-stage anvils in KMA (Fig.1b). A
variety of WC products are commercially available, and choosing a right product depending on
the purpose of the experiment is quite important. Efficiency of the pressure generation critically
depends on the hardness of WC, as well as on the truncated edge length (TEL) of anvils, and
pressures even as high as 50 GPa can now be produced by using harder WC anvils (Fig.3a,b,c) 6.
Figure 3. Efficiency of pressure generation using various WC anvils with TEL=3.0 mm (a) and TEL=1.5 mm (b), and the
plastic deformations of the anvils after compression (c)6.
Sintered diamond (SD) is much harder than WC and has been used as the second-stage anvils
for experiments above 30 GPa. Pressures even exceeding 100 GPa have been reported in KMA
with SD anvils4. However, its use as the anvils has been limited in very few laboratories, as these
anvils are quite expensive (~2000-3000 US$ each for 14 mm cubes) and also precise alignment of
the first-stage anvils is required, which is only realized with specially designed DIA-type
apparatus.
3. High pressure and high temperature generation
The efficiency of the pressure generation depends largely on the materials and sizes of the
gaskets and pressure medium using the same WC product as the second-stage anvils.
Pyrophyllite is generally used as the gaskets, which confine high pressure in the pressure
medium. The gaskets increase the strength of anvils by the lateral support principle, which
realize such pressures as several times greater than the strength of the anvils. Crushable semisintered ceramics, such as MgO, is used as the octahedral pressure medium, which is squeezed
via the truncated triangular surfaces of the anvil cubes (Fig.1b).
Pressures in KMA are evaluated by pre-determined relations between applied press load and
achieved pressure. Such pressure calibration curves are constructed for the cell assemblages with
53
various dimensions, based on the phase transitions in some reference materials whose pressures
are well documented. The phase transitions in Bi, Ba, ZnTe, ZnS, GaAs, and GaP are frequently
used for the pressure calibrations at room temperature, while those in SiO2, MgSiO3, and
Mg2SiO4 are used for those at high temperatures5,7.
Pressures can be more accurately determined from unit-cell volumes of some reference
materials, such as Au, Pt, NaCl, and MgO, using their P-V-T equations of state (EoS), when in
situ X-ray diffraction measurements are possible5,7. This can only be made at synchrotron
beamlines having adequate large-volume press with DIA-type guide blocks or equivalent systems.
It was noted that different P-V-T EoSs of these materials can lead to significant differences
(~10% of the nominal values) in pressure estimation at pressures greater than some 20 GPa, but
those using more recent EoSs agree reasonably (<~5%) well with each other at pressures to the
Megabar regime7.
A graphite tube heater is usually used for high temperature generation in KMA at pressures up
to ~10 GPa. However, the transformation of graphite to diamond hinders stable heating of the
sample at higher pressures, and other heating materials are used under such pressures. These
include LaCrO3, TiB2, B-doped diamond etc., and some refractory metals such as Re, depending
on the purpose and method of the experiment, some of which can maintain the sample
temperatures as high as 3000K for a few hours. Temperatures are measured with a thermocouple
and some metals or graphite are used as the sample container. An example of the cell/furnace
assembly used for the in situ X-ray observations with KMA3 is shown in Fig.4.
Figure 4. Examples of cell assembly (a) and furnace assembly (b), and X-ray radiographic images of the furnace assembly
as a function of pressure (c) for in situ observations in KMA using SD anvils3.
4. Applications to mineral physics studies
Phase relations and associated chemical changes in coexisting phases for minerals and rocks
have been studied mainly by quench experiments in KMA, as the crystal structures of most of
the high-pressure polymorphs of the silicates that constitute the Earths interior are preserved to
the ambient condition upon the release of pressure after the heating is terminated. Precise phase
relations in mantle rocks and subducting slab materials, as well as the minerals that constitute
54
these lithologies, have been extensively studied with KMA at the pressure and temperature
conditions corresponding to the upper parts (~1000 km) of the lower mantle of the Earth7.
The very first KMA installed at the synchrotron beamline in early 1980s, named MAX-80 and
operated in a 500 ton press at KEK in Japan8, opened the door to accurate determination of
phase boundaries based on in situ X-ray diffraction measurements under high pressure and high
temperature. A significantly larger KMA with 1500-ton press capacity9 was constructed at
SPring-8, one of the third-generation synchrotron light sources in the world, for in situ X-ray
observations. In situ X-ray observations at pressures greater than 20 GPa and temperatures
above 2000K were achieved soon after this beamline was operational10, and since then a number
of studies have been made on the determinations of phase boundaries, P-V-T EoSs of high
pressure phases, and the measurements of viscosities, structures, and densities of melts under
pressure by various techniques. The large KMAs have also been installed at the high-pressure
beamlines in many synchrotron facilities, such as APS, ESRF, Soleil, NSLS, HASYLAB and
PETRA-III, etc., and are now commonly used in the world.
Measurements of some physical properties of minerals are important to constrain the
composition and dynamics of the Earths deep interior, and the KMAs at the synchrotron
facilities greatly contributed in this direction. One of such studies is accurate measurements of
sound velocities of high-pressure minerals at high pressure and high temperature, by a
combination of ultrasonic pulse-echo measurements and in situ X-ray observations11,12 (Fig.5),
which effectively constrain the chemical compositions of deep mantle via a comparison with
seismologically observed sound velocities. Another recent progress is using deformation DIA (or
D-DIA) apparatus for studying rheological properties of mantle minerals/rocks, which provide
important clues to the dynamic processes in the mantle and subducting slabs13.
Figure 5. A set-up for sound velocity measurements in KMA at SPring-8 (a)11, and an example of measured ultrasonic
sound velocities (Vp, Vs) of high-pressure garnet as functions of pressure and temperature12.
5. Applications to novel materials synthesis
KMA has been used as virtually the only tool to synthesize materials with certain dimensions
(>1mm) at the ultrahigh pressures greater than 10 GPa with accurately controlled pressure and
temperature. Single crystals of high-pressure phases large enough for some studies, such as
55
crystal structure analyses and measurements of some physical properties, have been made with
advanced KMA technology. However, such crystals are generally limited to far less than 1 mm,
and difficult to be used for some other scientific purposes and industrial applications.
We have recently developed techniques to synthesize high-quality sintered polycrystalline highpressure phases with certain dimensions (up to about 1 cm) using KMA at high pressure and
high temperature. Outlines of these techniques and the characteristics of thus obtained sintered
polycrystalline high-pressure phases are reviewed here.
5.1 Superhard materials
High-pressure and high-temperature synthesis of single crystal diamond has been made under
the conditions close to the graphite to diamond phase boundary (e.g. 5.5 GPa, 1800K) by using
some solvents/catalysts. Although diamond is the hardest known material (Knoop hardness of
Hk = 60-130 GPa14, depending on crystallographic plane and direction), single crystal diamond is
rather fragile as it can readily be cracked along specific crystallographic planes. In contrast,
natural polycrystalline diamonds, such as carbonado and balas, are tougher than single crystals,
as development of such cracks (or dislocations) can be blocked by the grain boundaries.
Attempts to produce sintered bodies of pure polycrystalline diamond from diamond powders
have been unsuccessful, as the diamond is too hard to be sintered by conventional sintering
techniques. Thus, commercially available SD is produced with some binders, such as Co and
Si(C). Although these SD products are harder than WC, their hardness is generally limited to Hk
= 50-60 GPa.
Pure polycrystalline diamond was shown to be synthesized at very high pressures and
temperatures, typically 15 GPa and 2600K, in KMA by direct conversion from graphitic carbon15,
16
(Fig.6a). Such diamond was found to consist of very fine grains of diamond with diameters of
10-20 nanometers (Fig.6b), and was named as nano-polycrystalline diamond (NPD). Moreover,
NPD was found to have homogeneous hardness of about Hk=140 GPa15, which is even harder
than single crystal diamond. It was also found that NPD is tougher and thermally more stable
relative to single crystals.
Figure 6. A pressure vs temperature diagram showing the reaction boundaries of formation of nano-polycrystalline
diamond, NPD, and other forms of carbon (a). A TEM image of the NPD synthesized at about 15 GPa and 2600K15.
56
Efforts have been made to synthesize NPD with higher quality and larger dimensions, and the
NPD rods of 1 cm in both diameter and length are now routinely produced in our laboratory
using a KMA (BOTCHAN-6000) operated in a VLP (Fig.7a,b). The NPD was found to be easily
cut by a pulsed laser to basically any shapes, which have been successfully used for some
industrial applications, as well as for scientific tools such as anvils for diamond anvil cell7 and
KMA (Fig.7c)
Figure 7. A 6000-ton press KMA (BOTCHAN-6000) at the Geodynamics Research Center (a). NPDs synthesized with
BOTCHAN-6000 (b), and those cut to anvil cubes for higher pressure generation in KMA (c).
Since the successful synthesis of NPD, similar high-pressure and high-temperature synthesis
techniques have been adopted to produce polycrystalline hard materials using KMA. These
include aggregated diamond nanorod (ADNR)18, nano-polycrystalline stishovite (NPS) 19,
polycrystalline -boron20, nano-twined cBN21, etc. Although some of these superhard materials
are claimed to be even harder than diamond, none of them have been tested its performance in
actual applications as bulk materials.
5.2 Transparent ceramics
Transparent ceramics are important for applications to some optical devices because of their
superior mechanical strength and easier productions relative to those of singe crystals22.
Moreover, such specimens as high-quality and transparent polycrystalline samples of high
pressure phases are important for measurements of some physical properties of high-pressure
minerals of geophysical interest. Hot Isostatic Pressing (HIP) or Sparkling Plasma Sintering
(SPS) techniques at relatively low pressures (<1 GPa) have been used to synthesize transparent
ceramics, but with limited success because of difficulty in removing light-scattering sources such
as pores. Moreover, synthesis of transparent ceramics with nano-crystals (grain sizes of less than
100 nm) has never been reported using these techniques, although such ceramics are predicted
to have high optical transparency even for non-cubic materials23.
Attempts to produce transparent ceramics have been made in our laboraotry, using the KMA
techniques similar to those adopted in the synthesis of NPD, but faild to synthesize nanopolycrystalline transparent minerals24, except for diamond and cBN. More recently, bulk glass
samples with the compositions of some silicate garnet end-members and their solid solutions
have been used as starting materials, which suffered pressures from 5 to 15 GPa, at temperatures
57
1173-1973K for two hours25. Every efforts have been made to remove the effect of absorved
water, which causes pores, weaker grain boundary coheasion, and grain growth.
Figure 8. Highly transparent nano-polycrystalline silicate garnets with various compositions (a) synthesized with
BOTCHAN-6000. A TEM image of nano-polycrystalline grossular synthesized at 15 GPa, 1673K, with grain sizes of ~50
nm (b).
Highly transparent polycrystalline garnet has been obtained at limited temperatures and at
higher pressures (Fig.8a). Those with grain sizes less than 100 nm were obtained at pressures
greater than 10 GPa and temperatures around 1673K (Fig.8b), depending on the chemical
compositions, which exhibit optical transparencies comparable to those of corresponding single
crystals in the visible light region. The formation of nano-polycyrstalline garnet (NPG) is due to
a combination of rapid necleation of garnet crystallite, followed by slow grain growth under such
high pressures and the modest temperatures. This pressure-assisted synthesis technique of
nano-polycrystalline minerals in KMA could also be applied to the synthesis of other transparent
ceramics, which may lead to novel materials applicable to some optical and photonic devices.
Conclusions
KMA now covers pressures to the Mbar regime and becomes the major tool for high-pressure
Earth sciences in accurate determinations of phase transitions and some key physical properties,
complementary to diamond anvil cell. KMA also plays an important role in synthesis of novel
functional polycrystalline materials utilizing its relatively large sample volumes and stable
generation of high pressure and high temperature.
Acknowledgments
I am grateful to the following persons, who are current and past members of GRC, for
collaborations in developments of KMA technologies, their applications to various studies, and
characterizations of synthesized materials: Toru Shimei, Hiroaki Ohfuji, Takehiro Kunimoto,
Takeshi Arimoto, Koji Kawakami, Zhaodong Liu, Norimasa Nishiyama, Yu Nishihara, Toru
Inoue, Tomohiro Ohuchi, Masayuki Nishi, Takaaki Kawazoe, Jiaqian Qin, Li Lei, Yoshinori
Tange, Yuji Higo, Hitoshi Sumiya, Daisuke Yamzaki, Ayako Kurio, Kohei Wada, Futoshi Isobe,
Yoshio Ichida, Kiyoshi Fujino.
58
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60
Synchrotron X-ray Diffraction Techniques, and Complex Structures of the Elements
Synchrotron
X-ray diffraction techniques, and complex structures
Malcolm
McMahon
of the elements
mim@ph.ed.ac.uk
www.mimcmahon.com
Malcolm McMahon
School of Physics & Astronomy, The Univ. of Edinburgh, Edinburgh, UK

mim@ph.ed.ac.uk
www.mimcmahon.com
Abstract
A key finding of high-pressure diffraction work conducted in the 1990s was that the structural
behavior of the elements was much more complex than previously believe. Here I use a number
of different studies of elements to illustrate what is now possible using modern detectors and
synchrotron sources. Finally, I speculate as to what crystallographic studies might become
possible over the next decade.
Keywords
High-pressure, crystallography, crystal structure, elemental metals
The Elements at Ambient Conditions
The elements are the most fundamental materials and their high-pressure behaviour has
attracted the attention of many researchers since the pioneering work of Bridgman in the first
half of the 20th century1. At ambient conditions, the majority of the solid, non-molecular
elements adopt very simple high-symmetry structures, many of which are body-centred cubic
(bcc), cubic close-packed or hexagonal close-packed.
At high pressures we might expect that these structures would merely compress and that those
elements whose structures were not yet close-packed or bcc would become so. However,
differences in the density dependence of electronic energy levels can change the nature of the
bonding such that there are structural transitions to phases with lower symmetry and lower
packing density than found at ambient pressure. Changes of structure and electronic energy
levels can also give rise to dramatic changes in physical properties2. Applying pressure can also
induce transitions from molecular to non-molecular structural forms3, convert graphite into
diamond4, and polymerise simple molecules such as N25. In this lecture, I will confine myself to
elements that are metallic prior to compression.
Reviews of our knowledge of the high-pressure behaviour of the elements as of 1976 and 1991
can be found in refs 6 and 7, respectively. The majority of the high-pressure phases successfully
studied at that time involved transitions to simple, high-symmetry (cubic, tetragonal or
hexagonal) structures, although there were already known to be a significant number that
appeared more complex and resisted attempts at solution7. There were also a number of highpressure phases, such as Bi-III8, whose published structures did not provide as good a fit as might
be expected to the data.
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The Breakthrough of the 1990s

The introduction of image-plate area detectors in Japan in the early 1990's opened up a move to
angle-dispersive powder-diffraction (ADXRD) methods9 which were then developed at the SRS
synchrotron in the UK10 into powerful techniques that exploited both the higher resolution of
ADXRD methods and also the potential of an area detector to give accurate peak intensities,
making full-profile (Rietveld) refinement of high-pressure phases routinely possible for the first
time11. This approach has since revolutionised high-pressure structural studies using powder
diffraction methods and led to much new work on the elements to 300 GPa by the end of the
millenium, as reviewd in Ref 12. However, the structural complexity discovered by these studies
was such that powder methods were, within 10 years, unable to determine the structures,
requiring the development of new single-crystal techniques. These have subsequently been used
to show that elements can adopt structures with 8413, 10414 or even 76815 atoms per unit cell, or
structures that are incommensurate in one or more directions, and therefore never repeat16-18.
Experimental Methods
The methods we have used to study the metallic elements under pressure are powder and singlecrystal diffraction using synchrotrons radiation, the general details of which can be found in my
first lecture. However, many studies used a combination of the two techniques, and in some
cases the single-crystal diffraction did not require the collection of large numbers of Bragg
reflections. Indeed, the intensities of the reflections were sometime not needed at all. To
demonstrate the different methods, Ill describe the results from three different pieces of work.
Incommensurate Te
The high-pressure behaviour of tellurium exhibits many of the phenomena induced in materials
by compression. It undergoes a pressure-induced semiconductor-metal transition1; it has
numerous high-pressure phases19; it becomes a superconductor with a Tc that is highly pressure
dependent20; and it has an unusual melting curve21.
These features have prompted a wide range of resistivity1, diffraction19,22-25, density26, optical27,
superconductivity20,28 and theoretical29 studies. Despite all of these, the actual crystal structures
of the high-pressure phases had long remained unclear. In particular, the structures of Te-III,
reported to be stable between ~7 and 10.6 GPa, and Te-IV, stable between 10.6 and 27 GPa, were
unclear, with Te-III being reported as orthorhombic and Te-IV as rhombohedral19.
However, more recent studies reported that Te-III and Te-IV were one and the same phase, and
that this was monoclinic30, although numerous weak diffraction peaks still remained
unaccounted for. This story could be applied to many other elements as of 19907.
A synchrotron ADXRD pattern from Te-III at 8.5 GPa is shown in Fig. 1. Despite the quality of
the pattern (sharp peaks on a low background), we were completely unable to index all the peaks
in the pattern despite very many attempts. However, it was trivial to show that all previous
structural propositions were wrong. It is easy to show that a structure solution is wrong, it is
much more difficult to find the one solution that is correct.
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Figure 1. Diffraction profile collected from Te-III at 8.5 GPa. The tick marks beneath the profile identify those
reflections that are explained by the body-centred monoclinic unit cell.
On further compression we noticed that some peaks reduced in intensity, while others coalesced
into single peaks. Indexing of only the latter revealed that their positions were all accounted for
by a small body-centred monoclinic unit cell with lattice parameters a=3.919 , b=4.733,
c=3.062, and =113.517. But this solution still left some 16 peaks unaccounted for (Fig. 1). All
attempts to fit these reflections as a different phase, or as superlattice, were unsuccessful.
Figure 2. Part of the 2D diffraction pattern obtained from a twinned single-crystal of Te-III at 7.4 GPa. The main body-
centred monoclinic reflections from the two twin components are shown, indexed (hkl)1 and (hkl)2. The satellite
reflections are marked with asterisks, and a powder line from the tungsten gasket is marked G. D marks a reflection
from one of the diamond anvils.
By 9 GPa, tellurium has passed through two first-order phase transitions. Despite this, we loaded
a single-crystal of Te-I with the aim of obtaining a single-crystal of Te-III that we could use to
obtain more structural information on the phase. After 29 attempts, we finally succeeded in
obtaining a single-crystal of Te-III, a diffraction pattern from which is shown in Fig. 2. It was
immediately clear that the strongest Bragg peaks were those from the small body-centred
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monoclinic cell, while the weaker satellite reflections were the same as those we were unable to
account for in the powder data. Analysis of the positions of these satellite peaks revealed they
were all located at (h,kq,l) relative to the main Bragg peaks, with q ~ 0.3: Te-III is
incommensurate17. Note that a full single-crystal data set was not collected from the Te-III
crystal, nor was it necessary. The single image in Fig. 2 was sufficient to determine the
incommensurate nature of the phase.
Figure 3. Rietveld refinement of incommensurate Te-III at 8.5 GPa. The upper and lower tick marks below the profile
mark the peak positions of the main and first order satellite reflections, respectively.
Once we identified Te-III as incommensurate, all subsequent analysis was conducted using
powder-diffraction data using the formalism of 4D superspace31, and the JANA2000 software for
structure refinement32. A Rietveld refinement of the incommensurate Te-III diffraction profile is
shown in Fig. 3, and the modulated structure is shown in Fig. 4. Tellurium was only the second
element found to have a modulated crystal structure at high-pressure, the first, in iodine, having
been discovered 5 months previously33. The incommensurate Te-III structure has since been
found in selenium34,35, and in sulphur35,36. Sulphur was the first element shown to have an
incommensurate form above 100 GPa.
Figure 4. Four unit cells of Te-III at 8.5 GPa, as viewed down the a axis. The six nearest-neighbour contact distances for
each atom are shown, and those atoms at the body centres are labelled with 1/2. The modulation wave is indicated by
the dotted lines.
Incommensurate Sc
Scandium, the first of the 3d transition metals, undergoes a phase transition to Sc-II, at 21 GPa,
the structure of which has long been uncertain, despite the simplicity of its diffraction patterns.
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The structure was initially reported as tetragonal37-39, or cubic, with a structure comprising
unusual icosahedral clusters40.
Figure 5. Diffraction profile from Sc-II at 23 GPa. The tick marks show the calculated peak positions for the best-fitting
body-centred cubic cell40. The inset shows an enlarged view of the low-angle part of the profile, highlighting the doublet
peak at 2 ~ 11.1 which is not accounted for by the cubic unit cell.
Again, it was easy to show that none of these structures was correct (Fig. 5), but not determine
the true structure. In 2005, Fujihisa et al.41 solved Sc-II as having an incommensurate hostguest
(H-G) composite structure very similar to that we had reported in high-pressure Ba-IV, Sr-V, BiIII and Sb-II16,42,43. This structure (Fig. 6) comprises a tetragonal host structure that contains
channels running along the c-axis. Contained within these channels are 1D chains of guest
atoms that comprise the guest structure, the spacing of which is incommensurate with the host
along c.
Figure 6. The composite incommensurate structure of Sc-II, as viewed down the c axis. The eight-atom host framework
is shown in grey, and the 1D guest chains are shown in black. The insets show perspective views of (a) the body-centred
guest structure of Fujihisa et al.41 and (b) the C-centred guest structure of McMahon et al.44
However, close analysis of the H-G structure reported by Fujihisa et al.41 showed a worryinglyshort bond length a problem recognised by Fujihisa et al. Analysis of our own Sc-II powder
data revealed that an almost identical fit could be obtained by a H-G structure comprising the
same host structure as Fujihisa et al., but with a completely different symmetry for the guest
structure44. This structure did not have the short bonds of the Fujihisa structure. Despite the two
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guest structures having very different unit cell parameters, symmetries and densities, peak
overlap of host and guest reflections meant that they have almost identical powder-diffraction
patterns.
However, the two guest structures could be distinguished trivially using single-crystal data, as
their diffraction patterns would be completely different, even though the two phases have very
similar d-spacings (Fig. 7). But how to obtain a single crystal of Sc-II?
Figure 7. The (h0l) reciprocal lattice planes of the composite structure of Sc-II, with (left) the C-centred guest structure
of McMahon et al. and (right) the I-centred guest structure of Fujihisa et al. The host reflections are shown in black, and
the guest reflections in white. The host and guest reflections are superimposed along (h00) in both structures.
Sc is a hard transition metal, and diffraction patterns from Sc-I gave perfect powder patterns.
However, the diffraction rings from Sc-II were always slightly spotty, suggesting partial
recrystallisation of the sample at the transition. Compressing a small piece of Sc in He revealed
significant recrystallization at the transition, such that layer lines of reflections were clearly
visible in the Sc-II diffraction patterns (Fig. 8). These had the very distinctive pattern of
diffraction peaks from a H-G structure, and analysis of the reflections from the guest component
of the structure revealed them to be completely consistent our guest structure44 rather than
Fujihisas41.
Figure 8. 2D diffraction pattern from a quasi-single-crystal of Sc-II at 48 GPa. The relative spacing of the layers of
reflections from the host (hkl)H and guest (hkl)G structures (compare to Fig. 8), and the presence of the (001) guest
reflection confirms the guest structure to be C-centred.
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This study revealed that despite the extremely high quality of powder data now obtainable at
high pressures using ADXRD techniques at synchrotrons, the unavoidable problems of peak
overlap remains. The study also revealed that recrystallisation can occur at phase transitions,
even in hard metals ~1500 K below their melting temperatures, suggesting that single-crystal
studies may be possible in other systems hitherto thought to be inaccessible to such techniques.
Single-Crystal Studies of Sodium above 100 GPa
Sodium has the bcc structure at ambient conditions, and is a textbook example of a free-electron
metal. Predictions that Na would undergo a metalinsulator transition at pressure close to 100
GPa45 were followed by powder diffraction studies to above 100 GPa, which revealed transitions
to low-symmetry structures46-48 similar to those seen previously in Li49. In addition, studies of the
melting temperature found that the melting temperature of Na at 118 GPa was only ~300 K47.
Such behaviour is (currently) unique to sodium, and enabled us to grow high quality singlecrystals of the six different crystalline phases, four of which are unique to sodium, directly from
the melt. Four of these phases are extremely complex, with tetragonal, orthorhombic,
monoclinic and triclinic symmetries, and with approximately 52, 120, 512 and 90 atoms,
respectively, per unit cell50. Determining the lattice types and lattice parameters of these
complex structures would not have been possible using powder methods. However, the
availability of high quality single-crystals of each phase meant that we were able to obtain this
information with confidence, although full solution of these four structures will require further
experiments.
Figure 9. A diffraction image from the H-G phase of Na at 130 GPa, obtained using a 10 oscillation. Eighteen
reflections from the host component of the structure are shown indexed. Those reflections marked with a D are from
the diamond anvils. A section of the pattern, (b), has been replaced with a long-exposure non-oscillated diffraction image
collected in the same orientation and with its contrast enhanced to reveal the first layer of very weak, elongated
reflections from the guest component of the structure.
Above 125 GPa sodium transforms to a phase with very low optical reflectivity. A diffraction
pattern from this phase is shown in Fig. 9, and contains characteristic lines of diffuse scattering.
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This, and the very-distinctive spacing of the Bragg reflections, reveal this phase to have an
incommensurate H-G composite structure, of the type found previously in Sc and other
elemental metals51. The structure is shown in Fig. 10, and comprises a 16-atom tetragonal host
framework, isostructural with that found previously in Rb and K52,53, but different to that found
in Sc, (compare Fig. 10 to Fig. 6). As in Sc, the host framework has channels along the c-axis that
contain chains of Na atoms. The disc-shaped Bragg peaks from the guest component of the
structure reveal it to be weak correlations between neighbouring chains.
Figure 10. The hostguest composite structure of the H-G phase of Na shown in projection down the c-axis. The host
atoms are shown in light grey and guest atoms in dark grey. The monoclinic guest component unit cell is outlined with
dashed lines, and a separate perspective view of the guest structure is shown.
The H-G phase of Na is stable to 190 GPa, where it transforms to a transparent insulating
hexagonal structure which calculations suggest contains distinct pockets of interstitial electron
density54. The experimental confirmation of the e-density pockets will require very high accuracy
diffraction data to be collected to high diffraction angles. This represents a substantial
experimental challenge for crystallographic studies, and remains beyond current capabilities.
Future Structural Studies of the Metallic Elements
What does the future hold for structural studies of the elements? A comparison of the phase
diagrams in Refs 7 and 12 shows the dramatic advances that were made in the 1990s, and which
have continued into the new millennium. But what about the next 10 years? The development of
the two-stage DAC55 opens the way for detailed structural studies to 1 TPa although we have
yet to see whether the lareg number of phase transitions that take place at lower pressures
continue to 1 TPa and above. Structural studies at pressures above 1 TPa will also take place via
dynamic compression of samples. The National Ignition Facility is already accessing pressures in
the multi-TPa regime. As always, determining the crystal structure at these conditions will be
crucial, and predicting the structures of simple materials at these pressures has already produced
some interesting results, including a six-coordinated cubic host-guest phase of lithium56 and an
incommensurate phase of aluminium57. The advent of ultra-bright x-ray beams from x-ray free
electron lasers (XFELs) means that studying the crystallography of matter at such conditions is
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no longer beyond the realms of imagination, and promises many new discoveries over the
coming decade.
Acknowledgements: I would like to thank and acknowledge the numerous colleagues and
collaborators who have contributed to the research and developments published by our group
over the past 20 years that I have cited in this review. I would also like to thank facility staff at
synchrotron and neutron sources for their assistance and support in the experiments and
technical developments. This work was supported by grants from the Engineering and Physical
Sciences Research Council and the Royal Society, and facilities and funding provided by SRS
Daresbury Laboratory, the European Synchrotron Radiation Facility, the Advanced Photon
Source, and Diamond Light Source.
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71
Neutron Diffraction
NeutronSpallation
diffraction
Malcolm Guthrie, European
Source
email: malcolm.guthrie@esss.se
Malcolm Guthrie
homepage: www.europeanspallationsource.se
European Spallation Source, Lund, Sweden
malcolm.guthrie@esss.se
www.europeanspallationsource.se
Abstract
To many crystallographers, neutrons are a less familiar tool than x-rays. Yet their many
advantages for high-pressure diffraction have long been recognised (indeed the first ever highpressure beamline was actually built at the Idaho Falls Research Reactor in the 1960s). The key
attributes of neutrons - their sensitivity to light elements, their deep access to reciprocal space
and their ability to measure magnetic structure have been of limited use for high-pressure due
to the lack of bright sources. However, the commissioning of two major new neutron facilities in
the USA and JAPAN within the last decade, upgrades at mature facilities and the on going
construction of the future European Spallation Source in Europe, may underpin rapid expansion
of high-pressure neutron science. Here, the key advantages of neutrons and measurements
using these under extreme pressures will be described.
1.1 Introduction
The fundamental physical processes of crystallography using neutron radiation are identical to
those of x-ray radiation [ref McMahon lecture 1]. That this is the case is directly attributable to
wave-particle duality of the neutron, which allows scattered neutrons to interfere and give rise to
both Bragg peaks and diffuse scattering that encapsulate information on atomic structure.
However, it is the intrinsic properties of the neutron particles themselves that convey important
advantages to the neutron crystallographer.
Here, the many advantages of neutron techniques will be outlined with a focus on their specific
application for in situ high-pressure crystallography. Starting with the fundamental properties of
the neutron, we will consider their generation, control and detection. The nature of neutrons
and neutron sources has important consequences for the instrumentation used for high-pressure
crystallography, which will also be explored.
An important context is given by recent investments in new neutron facilities around the world.
These new and brighter sources have already begun to revolutionise the field, a trend that looks
set to continue with future, even more powerful, sources such as the European Spallation Source
on the horizon.
1.2 The neutron: a tool for crystallography
The neutron is a massive particle that is electrically neutral, with a spin of and an intrinsic
magnetic dipole moment. As a consequence of its electrical neutrality, the neutron is able to
72
penetrate deep into the core of atoms where it interacts directly with sample nuclei via internuclear forces. These nuclear forces have a complex dependence on the nuclear species, so even
chemically identical isotopes may scatter differently. This interaction, for the purposes of
diffraction, is measured by the coherent neutron cross-section shown in Figure 1, where it is
contrasted with x-rays, whose scattering strength is dependent only on the number of electrons,
Z.
Fortuitously, many of the weakest x-ray scatterers (H, Be, B11, C, N, O and F) happen to be strong
scatterers of neutrons, making both techniques highly complementary. This is particularly useful
in studies of systems that combine very heavy and very light atoms, for example the transition
metal hydrides or nitrides, many perovskites and systems, such as H2S, recently shown to exhibit
superconductivity at an unprecedented 190K1. Another important experimental application of
the variability of the neutron scattering strength is to obtain diffraction contrast. An example
with direct relevance for mineral physics2,3 is given by the atoms Mn and Fe, which differ by only
1 electron (a ~4% difference in their relative x-ray scattering cross-sections), but have neutron
scattering cross-sections that differ by 540%. This application of neutrons for probing the
relative distributions of Mn and Fe atoms has been recognized since at least 19564. Finally, as the
cross-section is dependent on the specific isotope, it is also possible to obtain diffraction contrast
between chemically identical atoms and this has been used extensively in structural studies of
glasses and amorphous systems to deconvolve partial pair-correlations since its first application
in 19665.
Figure 1. Comparison of neutron scattering cross-sections and atomic number for the first 26 elements.
The extremely short range of the neutron-nucleus interaction (~ fm) also means that the
scattering centres are perfectly point-like on the ~ 1 length scale of the wavelengths used for
crystallography. This is quite different from the case of x-rays, where the scattering centre is the
extended electron cloud, which is also of order 1 in size. This has an important effect, which
becomes apparent if we consider the Fourier relationship between the real space structure and
reciprocal space diffraction intensities. We can represent the extended crystalline material as the
mathematical convolution of the scattering objects themselves (i.e. the physical contents of the
unit cell: atoms and molecules) with an infinite mathematical lattice. The scattering objects can
be represented by as a density distribution (r), which is a function of vector position r in real
73
space. Meanwhile, the lattice L can be represented by a 3D array of Dirac -functions of the
, where the specific values of r are obtained at integer multiples of the crystal lattice
form
parameters a,b and c. So that:
(1)
The crystal structure C(r), is then given by the convolution of these two functions, which can be
written as
The measured diffraction pattern D(Q) - intensity measured as a function of location in

reciprocal space Q is, essentially, the Fourier transform
of the crystal structure, so:
(2)
Where the last line follows from the convolution theorem. So, the diffraction pattern is given by
the product of the Fourier transform of the real space lattice (also an infinite lattice) and the
Fourier transform of the scattering density (r).
In the case of x-rays, where (r) represents the electron clouds themselves, which are extended in
space,
is a function that decays rapidly with as a function of Q. As the diffraction
pattern of the lattice is multiplied by this decaying function, the x-ray Bragg intensities also
decay rapidly as the magnitude of Q increases. This well known effect, is called the atomic form
factor and is an indirect measurement of the shape of the electronic distribution.
However, for neutrons, (r) is not extended (relative to the wavelength of the radiation) but is
comprised of a collection of point-like nuclei, which, like the lattice itself, can be represented by
a summation of Dirac -functions. The Fourier transform of a -function is simply a constant
and so is Q independent and so Bragg intensities do not decay at higher momentum transfers.
This simple physical fact means that neutrons can probe much more deeply into reciprocal space
than x-rays. Again, Fourier considerations show that this leads to a much higher real-space
resolution for neutrons than can be achieved with x-rays. This is invaluable in studies of thermal
motion, multi-site disorder and makes neutrons the technique of choice for studies of local
structure in non-crystalline systems such as liquids and glasses. In this latter situation, where
radial-distribution functions are obtained from the total scattered intensity, the limiting realspace resolution is simply given by 2/Qmax where Qmax is the magnitude of the highest
momentum transfer that reliable intensities can be measured.
Lastly, and of equal significance to the attributes above, each neutron possesses its own intrinsic
magnetic moment. Therefore, the neutron will interact with, and scatter from, any magnetic
74
atoms in the material being studied. In the case of a material with crystallographic magnetic
order, this simply gives rise to additional Bragg peaks that are purely magnetic in origin. These
magnetic peaks give a direct measurement of extended magnetic structure that is unique to
neutrons. It is important to remember that, in contrast with scattering by nuclei, magnetic forces
do extend over large distances. Consequently, the magnetic Bragg intensities are affected by a
strong magnetic form-factor that is directly analogous to the x-ray case described above and are
typically only visible at low magnitudes of Q.
1.3 Neutron production, detection and the beamlines
Despite their many advantages, neutrons come with their own unavoidable challenges. Firstly,
only relatively weak sources are available. Neutron sources used for research are generated using
two techniques: nuclear fission (in the case of reactor sources) and spallation (in the case of
accelerator-driven sources). Although fusion reactions can produce significant neutron yields6,
sources exploiting this are not yet technically feasible.
Fission reactors are driven by a controlled chain reaction: heavy nuclei are split into lighter
fragments, giving off mass and energy in the form of gamma radiation and neutrons. The
neutrons produced cause more heavy nuclei to split, generating still more neutrons in a positive
feedback loop. By inserting neutron-absorbing material into the reactor the reaction can be
controlled.
Figure 2. Brugger plot extended to show the flux of the most recently constructed sources and the future ESS source7.
Spallation sources operate in a quite different manner. They are driven by a particle accelerator 1 ,
that creates a beam of protons that is then slammed into a target material (a heavy metal such
as tungsten, or mercury in the case of the liquid target sources) chipping or spalling neutrons
from the target nuclei.
In both cases, the resulting neutrons have very high energies and need to be slowed down in
order to be useful for diffraction (and other) experiments. A device called a moderator achieves
1
The first spallation sources used synchrotrons that, in more than one case, were re-purposed from earlier particle
physics experiments. Meanwhile, most modern sources use linear accelerators, which are capable of reaching higher
energy levels.
75
this by causing multiple collisions between the nuclei and the moderator material. In each
collision, the neutron loses energy until it has thermalised that is, it has acquired an energy that
is characteristic of the temperature of the moderator. Depending on the application, different
moderators can be used, for example liquid water, liquid methane or solid hydrogen are all used
as moderator materials on different diffraction beamlines. The temperature of the moderator
defines the wavelength spectrum of the neutrons, which follows a Maxwellian distribution. The
neutron crystallographer can consider the moderator as their effective source of the neutrons.
A simple way to compare different sources is to look at the total flux that they produce, i.e. the
number of neutrons per unit area per second. This was first done by Brugger8 (in an article
simply entitled we need more intense thermal-neutron beams), in a form that has been
continually updated as new facilities come online. A recent version of the plot9 is shown in
Figure 2. This indicates that while reactor fluxes peaked sometime in the mid 1960s, spallation
sources continue to increase in power. The Brugger plot also shows that all of the sources
constructed in the last decade are spallation-driven, as will be the European Spallation Source
(ESS). This certainly reflects a move away from reactor technology, driven by concerns about
safety and waste, which were further exacerbated by the Fukushima-Daiichi nuclear disaster in
2011.
The key disadvantage of neutrons is also illustrated by Figure 2 when one considers that the
number of photons emitted by a 60W light bulb is ~ 1020 photons/s 2 ! In comparison, the ESS will
only produce 5x1017 neutrons/s at the peak intensity of its pulse. Worse still, unlike a
synchrotron, where undulators produce x-rays over a very narrow angular range (i.e. have a low
divergence), neutrons are distributed over all angles further diluting usable flux. Lastly, as the
neutron has no electric charge, it cannot be steered using magnetic fields or mirrors, it can only
be gently focused using grazing incidence scattering.
1.3.1 Neutron detection
The relatively low interaction of neutrons with matter can also make them difficult to detect.
Consequently, the technologies used to detect neutrons rely on secondary interactions which
either generate charged particles or light. All neutron detectors are based upon the small
number of nuclei with high absorption cross-sections (Table 1). The neutron capture results in
an excited state, which then decays by emission of the detectable species.
Table 1. Isotopes used in neutron detection10.
Isotope
Absorption cross-section (barn)
He
5333
Li
940
3835
3
6
10
Photons/s = P/hc, where P = power on watts, = wavelength, c the speed of light and h Plancks constant. For a 60W
bulb with median wavelength 600nm we would expect 1.81x1020 photons/s.
76
One important example of a neutron detector used for diffraction is the 3He tube. These contain
a gas of 3He whose nuclei absorbs neutron and then split into 1H and 3H ions. The resulting
excess charge can be detected with conducting wires in contact with the gas. These detectors
have a very high efficiency, due to the high absorption cross-section of 3He, and have a very good
ability to discriminate between neutrons and -rays. Their main disadvantage is the difficulties in
obtaining 3He, whose production is tightly controlled as it is linked to nuclear weapons
programmes. Alternative technologies based on 10B as an alternative are currently being
developed.
A second important class of detectors are those based on scintillation. These are based on the
detection of light photons (using photo multiplier tubes) that are generated by secondary
interactions triggered by a neutron event in materials such as 6Li-enriched glass. In designing
such a detector, usually a compromise is necessary in order to maximise the path length available
to the neutron (increasing the chance of an interaction event) and minimising the path length
for the resultant light to exit (increasing the chance that the light is detected). An inclined
geometry is one way to obtain a balance between these conflicting requirements.
1.3.2 Neutron sources for high pressure
There are many neutron sources around the World, but not all of these have strong highpressure programmes. Notable high-pressure work at reactor sources has been conducted at the
Laboratoir Lon Brillouin and Institut Laue Langevin both in France, Dubna in Russia, HFIR in
the US and the Opal reactor in Australia. Meanwhile, the three main pulsed spallation sources all
have dedicated high-pressure diffractometers: The ISIS Facility in the UK, The SNS Facility in
the USA and the MLF Facility in Japan. The European Spallation Source already has a highpressure platform in its sample environment group.
Figure 3. Neutron sources with significant high-pressure activity
1.3.3 Dedicated high-pressure beamlines
There are several advantages to building a neutron instrument that is optimised for
crystallography at high pressure. Although the majority of neutron facilities in the World are
able to run high-pressure diffraction experiments on a range of beamlines, there are only three
77
instruments, currently in operation, that are optimised for this extreme condition. All three of
these are based on pulsed sources and use the time-of-flight diffraction technique (Section 0).
PEARL, based at the ISIS neutron source is the most mature of the currently operational
dedicated high-pressure beamlines. It is optimised for operation with a Paris-Edinburgh press

using opposed toroidal anvils. The maximum accessible pressure is in the 20 GPa range and both
low and high-temperature inserts are available.
PEARL has a direct view of a liquid methane moderator (~110K) at a distance of ~15m. Its main
detector bank is centred on 2=90 and can access a d-spacing range of around 0.5 to 4.2 . The
two main advantages of a 90 bank are that the signal from the anvils can be minimized by
diffracted beam collimation and that the signal in all of the detectors can be easily summed to
improve counting statistics. However, a fixed angle limits access to reciprocal space, so PEARL
also has a second bank, lying in the plane parallel to the beam. The resulting access to low
diffraction angles increases maximum d-spacing to ~ 8 while the access to high diffraction
angle increases resolution for low d-spacing reflections.
PLANET is based at the MLF facility in Japan and is the youngest of the dedicated beamlines.
Although it is also based on a 90 scattering geometry, it is unique in having a large 6-axis press
enabling multi-anvil experiments. The entire press can also be translated downstream of the
sample position enabling other devices (such as Paris-Edinburgh and diamond-anvil cells) to be
used. PLANET has the longest flight path of all three instruments at 25m and views a decoupled
hydrogen moderator. The long flightpath, combined with a chopper assembly, allows both good
d/d diffraction resolution and flexible and broad wavelength coverage.
Figure 4. Three different high-pressure diffractometers. (From left to right) drawing of the PEARL diffractometer
showing its two perpendicular detector banks; the sample position of SNAP showing a laser-aligned collimator, beamdefining slits and extended detector snouts; the massive 6-axis press used on PLANET, Atsuhime.
SNAP based at the Spallation Neutron Source (SNS) was commissioned in 2008. It has a 15m
flightpath and has a direct line of sight to the SNS decoupled supercritical hydrogen moderator.
Out of the three instruments, SNAP has the most synchrotron-like appearance, with movable
detectors, a hexapod sample positioner and an optical bench for mounting components. The
detectors are able to move in the horizontal plane and can access diffraction angles from ~25 to
155. They can also both be positioned at 90 and the resulting counts summed. In addition to
Paris-Edinburgh cells (which are normally operated with a vertical axis and incident and
78
diffracted beams passing through the gasket), SNAP has also been the site of recent development
of powder diffraction measurements from DACs described in Section 0.
1.4 Exploring reciprocal space with neutrons
The key difference between fission reactors and spallation sources is that the former produce
neutrons in steady state, while the latter produce them in pulses 3 . As a general rule, angledispersive techniques are more common at reactor sources, where monochromators are used to
select a single wavelength (and its harmonics) from the moderator spectrum. Meanwhile, the
intrinsic timing structure of a pulsed source naturally lends itself to energy-dispersive
experiments using the time-of-flight (ToF) technique.
1.4.1 Time of flight diffraction
This useful technique exploits the fact that the velocity of the neutrons depends on their energy
and, consequently, is related to their wavelength, . The thermal neutrons used for diffraction
are non-relativistic, so is inversely related to their momentum p:
(3)
where mn is the neuton mass and v its momentum. As speed is given by distance (L) over time
(T), it follows that wavelength is also proportional to the time taken to travel a known distance.
(4)
Therefore, a high-energy resolution can be readily achieved by simply using high-precision
electronics timing synchronised with the spallation pulse.
ToF Resolution Optimising the diffraction resolution d/d the width of a Bragg peak divided
by its d-spacing - is often the primary consideration when designing a neutron instrument. For
ToF instruments this is encapsulated in the resolution equation, derived from Braggs Law:
(5)
The three terms on the right hand side encapsulate respectively the uncertainty in the scattering
angle (), time-of-flight (T) and flight path (L). The angular uncertainty is given by the
angular divergence of the moderator So, from the vantage of the sample position, it is possible to
see neutrons arising from any point on the moderator surface, each of which will be at a slightly
different angle. The total angular divergence can be readily estimated calculated angular size of
3
There are exceptions to this rule, the Joint Institute for Nuclear Research in Dubna has a pulsed reactor source, while
the Paul Scherrer Institute in Switzerland has a steady-state spallation source, SINQ.
79
the moderator: for a typical neutron moderator ~10x10cm, and a 15m flight path, this would be
~9 mrad. This divergence can decreased by reducing the visible area of the moderator (typically
using neutron absorbing jaws), however, this would be at the expense of flux. Conversely,
neutron focusing optics can be used to increase flux, at the expense of increased divergence.
The next term in the resolution equation, , reflects the uncertainty in the measured time of
flight. This arises as there is a finite time between the target pulse and the thermalisation of the
resulting neutrons in the moderator. The important quantity for diffraction measurements is the
ratio T/T. So, while should be constant for a given accelerator time structure and moderator
material, the total time-of-flight, T, can be increased by simply increasing the distance from
moderator to detector. Thus, high resolution ToF diffractometers, such as HRPD at ISIS have
beam flight paths ~ 100m, while diffraction instruments at the ESS, which will use a long-pulse
structure will have beamlines in excess of 150m. As described above, the three dedicated highpressure instruments have relatively short beamlines (<25m), compromising their resolution to a
certain extent. This is because, without a guide, the beam intensity will decrease according to the
1/r2 law. It is clear that robust neutron guide technology will be critical for high-pressure work at
the ESS. The final term in Equation 5 reflects the uncertainty in the total flight path. This is
simply due to the finite thickness of the moderator, and is typically a fixed constraint.
Choppers For crystallographic measurements, bandwidth of available neutron wavelengths is
clearly an important characteristic. While flux of neutrons at a given wavelength is determined

by the moderator properties, this is also limited by the pulse frequency. The effects are often
visualised using a time-distance plot such as the one in Figure 5, which shows that, as the
neutrons propagate, they disperse in time (the same effect encapsulated by the 2nd term in
Equation 5). The usable wavelength range is, thus, limited by the intrinsic period P of the source
and the flightpath L of the instrument (i.e. the distance from moderator to detector): at a certain
point in time, slow neutrons from a given pulse will be overtaken by fast neutrons from the
subsequent pulse. This problem, called frame overlap, would give rise to severe problems for
crystallography. Therefore, in addition to the fundamental parameters P and L, the wavelength
range is sometimes also controlled using a mechanical chopper. The chopper is a device
consisting of a rapidly spinning disk of neutron absorbing material with a slot that allows
neutron transmission for a defined time period. A chopper can be represented in the timedistance plot by a solid bar that is broken for fixed period of time to represent when the chopper
is open. Figure 5 shows the example of a chopper that defined limits of the fastest and slowest
neutrons that can reach the detector (and ensures no frame overlap). Another possible use of
choppers is to skip a frame, whereby every second frame is blocked, effectively doubling the
period of the source and allowing very slow, long wavelength neutrons to reach the detector.
80
Figure 5. time-distance plot illustrating the trajectories of neutrons at a pulsed source. The time at the origin
corresponds to the initiation of a pulse of the accelerator, which results in a burst of neutrons that lasts for the pulse
width, . Neutrons then travel from the moderator to detector at a constant speed that depends on their energy and is
given by the gradient of the trajectory line. A bandwidth chopper can be used to prevent frame overlap.
1.4.2 Comparing Time-of-flight and monochromatic experiments
The key differences between ToF and monochromatic diffraction measurements are evident if
we consider their distinct Ewald constructions (Figure 6). In the case of ToF diffraction, each
pulse of neutrons surveys the volume of reciprocal space within the boundaries of two Ewald
spheres corresponding to the maximum and minimum wavelengths accessible on the
diffractometer. As discussed above, it may be possible to tune these limits using choppers.
Meanwhile, in the monochromatic case, there is a single Ewald sphere and reciprocal space is
only sampled on its surface.
As ToF diffraction accesses a volume versus a surface, it is often possible to conduct experiment
using a much smaller angular detector coverage than in the monochromatic case. This can be
useful, especially for opposed anvil devices (see Section 0) or multi-anvil presses, where the
aperture for the diffracted beam is tightly constrained. On dedicated ToF diffractometers,
a common geometry is to use banks of detectors at 90 to the incident beam. Not only does this
make it possible to sum over a large proportion of the available azimuthal angle, this is also the
ideal angle to collimate out the signal from the upstream and downstream components of the
cell.
The main disadvantages of ToF are the relatively small time-averaged flux of a pulsed source 4
and the increased complexity of the wavelength-dependent corrections such as cell attenuation,
detector efficiency and sample dependent effects such as extinction.
Although the ESS will be the first pulsed source whose time averaged flux exceeds that of the most powerful reactors
81
Figure 6. Access to reciprocal space is illustrated using Ewald constructions for both time-of-flight (A&B) and
monochromatic experiments (C&D). The top two panels (A&C) show the a*-b* plane of the reciprocal lattice of
diamond, the lower two panels (B&D) show the equivalent reciprocal space construction for a powder sample, in the a*b* plane, this is a set of concentric circles centred on the origin of reciprocal space.
1.5 High-pressure instrumentation for neutrons
The low fluxes available on neutron sources mean that large sample sizes must be used in order
to access sufficient signal. Large sample volumes necessarily imply larger forces to achieve a
given pressure and, by and large, neutron pressure cells are substantially larger than their x-ray
equivalents.
1.5.1 High-pressure neutron cells
There are several different classes of pressure cell, which can be organised according to their
maximum sample size and their pressure performance. These are summarised in Table 2
82
Table 2. Summary of common high-pressure sample chambers

Cell type
Description
Current Max. pressure
Sample Vol (mm3)
gas
A thick walled cylinder through connected

to a high-pressure gas supply
<1
2000
clamp
A supported piston-cylinder-type device

where an applied force is locked in by a
clamping mechanism
2-3
2000
ParisEdinburgh/
TAP-98
An small <200 tonne capacity hydraulic

press used to force opposed toroidal anvils
together. The sample is contained by a
metal gasket
23
30-100
Multi-anvil
Only used on the PLANET beamline [ref], a

massive pressure compresses an assembly of
anvils. In a typical assembly, eight cubic
anvils with truncated vertices are placed
together such that the adjacent vertices
form an octahedral sample space
15
30-100
Gem-based
Opposed diamond or sapphire anvil cells

optimised for neutrons. The sample is
contained in a metal gasket
100
0.05
(GPa)
Construction materials The extreme mechanical stresses inside a pressure vessel often reduce
the engineering possibilities to a handful of materials. In the case of opposed anvil cells (such as
Paris-Edinburgh presses, the TAP-98 press and gem-based cells) and multi-anvil cells, it is
necessary to use an extremely hard material. There are several possibilities, which can be
grouped according to their microstructure. The most common polycrystalline materials in order
of increasing hardness are: alumina (a zirconium-toughened form is used), tungsten carbide and
sintered or (more recently) polynanocrystalline diamond. The two single-crystal materials that
have been successfully employed are sapphire and diamond 5 .
Equally important for opposed anvil cells is the choice of gasket material. Common choices
include TiZr null scattering alloy, copper beryllium and T301 stainless steel. TiZr is used almost
exclusively in cases where the beam may hit the gasket, however, it cannot be used with singlecrystal diamond anvils as it bonds to the diamond surface leading to failure. Common gasket
materials used for x-rays are tungsten or rhenium, however, both have very high neutron
absorption properties (18.3 and 89.7 barn at 2200ms-1respectively10) and are unsuitable where
the beam must enter or exit through the gasket.
In the case of the cylinder of a piston-cylinder cell, or the body of a gas pressure vessel, hardness
is still important, but this must be balanced with the need for high tensile strength. For
monobloc cylinders where a compromise must be reached in a single material, common choices
5
An initially promising alternative material, moissanite (SiC), was developed in the early 2000s as a high-pressure
anvil[ref Xu, Mao, science], however, it has not been widely adopted.
83
are aluminium (for very low pressure applications), copper beryllium, titanium-zirconium alloy
and high performance steels. It is possible to use harder materials in these cylindrical chambers,
however, it is then necessary to support the hard material with a secondary, high-tensile
material. Although this enables higher pressures it unavoidably entails a reduction in scattering
aperture.
The Cell Background An important aspect of all high-pressure vessels is the need for the beam
to enter and exit through the vessel itself. Unavoidably, this leads to an additional signal, the cell
background, which can be substantially larger than that from the sample and which must be
mitigated. The palette of materials described above each give their own characteristic
backgrounds. Clearly the most important factor is the scattering strength of a given material:
assuming equal density, stronger scatterers will give higher backgrounds. Table 3 shows the basic
neutron scattering properties of some of the most common pressure-cell materials.
Table 3. Neutron scattering properties of common pressure cell construction materials
Element
Coherent
Coherent cross
Incoherent cross
Absorption cross
scattering
section (barn)
section (barn)
section
At 2200ms-1 (barn)
length (fm)
C
6.646
5.51
0.001
0.0035
Al
3.449
1.495
0.0082
0.231
5.803
4.232
0.0008
000019
Ti
-3.438
1.485
2.87
6.09
Fe
9.45
11.22
0.4
2.56
Zr
7.16
6.44
6.46
0.185
Crystalline microstructure is also an important factor to consider. As seen in Figure 6, a

polycrystalline material is represented in reciprocal space by a set of concentric spheres. In the
polychromatic scenario of a ToF experiment, this means that each of the continuum of
wavelengths between the two limiting Ewald spheres will satisfy the Bragg condition at a given
2, corresponding to sheets of background scattering at constant d-spacing. In contrast, a singlecrystal material such as a diamond anvil will give rise to a background that is localised in
reciprocal space in the form of intense single-crystal Bragg spots.
In addition to coherent sources of background, a certain percentage of neutrons are scattered by
nuclear interactions that randomise their phase. The intensity of this incoherent scattering is
measured by the incoherent cross-section of the nucleus (4th column, Table 3). Incoherent
scattering is wavelength independent and spatially distributed. Some materials, famously
vanadium, have predominantly incoherent scattering and so give rise to only very weak Bragg
peaks. Yet another way to obtain a Bragg free background is to identify combinations of
materials that have negative and positive scattering lengths such that their contributions cancel.
Neutrons scattered by nuclei with a negative scattering length experience a phase change of
and so, when combined with a positive scattering material in a substitutional alloy, can cancel
84
out the coherent scattering. An example of the resulting null alloy is Ti0.68Zr0.32 in common use
as a gasket material for Paris-Edinburgh cells.
Lastly, -ray background may also be an issue for certain detector technologies. The production
of -rays can be substantial, and typically arises from neutron absorbing shielding or collimation.
This is because the energetic nuclear states arising as a result of neutron capture typically decay
via the emission of electromagnetic photons. The high energy of this radiation makes it difficult
to shield, requiring significant thicknesses of dense material such as lead.
Cell Attenuation A second important consideration is that of cell attenuation, which results in a
wavelength-dependent modification of the incident spectrum. This effect must be corrected in

order to obtain reliable diffraction intensities from the sample. In general, both the incident and
diffracted beams experience attenuation that is due to both the pressure vessel and the sample
itself. This attenuation has two main components: simple mass absorption (neutron capture) and
structured attenuation due to Bragg scattering. The first of these effects is the exponential
reduction in transmitted beam intensity that depends on the path length traversed in the
material and the density and absorption cross-section of the relevant nuclei. The second effect
Bragg attenuation is the result of losses in transmitted radiation due to Bragg diffraction as the
beam passes through the material.
In the case of a polycrystalline material, each reflection will be sampled by a continuous range of
wavelength according to Braggs law. The highest possible scattering angle of 180 gives the
maximum wavelength for a given d-spacing of max = 2d. Below this Bragg Edge the transmitted
beam will be attenuated. As each successive d-spacing creates a new edge, resulting in a sawtooth shaped attenuation that is most pronounced for strongly scattering materials (see Figure
7). The depth of each edge is dictated by the microstructure of the attenuator and is, in general,
difficult to calculate. Consequently, generating an attenuation correction for this effect usually
relies on experimental measurement of profiles such as those shown in Figure 7.
Figure 7. Attenuation due to sintered diamond anvils11.
85
In the case of a single crystal (such as a diamond anvil), the attenuation only occurs at specific
wavelengths, dependent on the orientation of the anvil. An example of the resultant dips in
transmitted spectrum as a neutron beam passes through the two diamonds in a diamond-anvil
cell is shown in Figure 8. As with the polycrystalline case, these dips must be measured
experimentally as their depth is determined by the mosaic spread in the crystal and is highly
dependent on the strain condition of the anvil (i.e. it varies with pressure).
Figure 8. Transmission through two diamond anvils. Both anvils are approximately aligned with the 100 axes parallel to
the beam, however, slight variation in this angle can cause the four [100] equivalents that satisfy the Bragg condition to
appear at different wavelengths. The vertical ticks above the spectra indicate predicted positions for the dips, determined
from the orientation matrix of the diamond.
1.5.2 Recent developments in neutron DACs
Diamond anvil cells are able to sustain the highest static pressures of any devices, however, their
small sample sizes have hampered their use at neutron sources. There have been some examples
of their use in high-pressure neutron research since the 1980s (primarily on reactor sources)
and, notably, pressures of up to 43 GPa were reached12. However, all of this work focused on the
measurement of a handful of strong peaks at low Q. At the corresponding longer wavelengths,
neutron sources are brighter, detectors and focusing optics more efficient and backgrounds are
much easier to control. While such measurements are useful, perhaps most importantly in
determining magnetic phase diagrams, they preclude quantitative crystallographic studies of
atomic structure.
Toward the end of the first decade of the century, two new spallation sources the SNS at Oak
Ridge National Laboratory and the MLF at the J-PARC accelerator complex in Japan began to
produce some of the brightest neutron pulses in history. These new flux levels, combined with
improvements in detector and focusing technologies have opened the way for the expansion of
DACs in neutron-diffraction measurements. This work has seen notable successes on the SNAP
86
beamline at the SNS, where quantitative diffraction measurements have been made up to almost
100 GPa13.
In addition to the brightness of the new sources, new cell designs were critical to conduct these
measurements (Figure 9). The minimum usable sample volumes, ~0.02mm3 are still over 100
times larger than traditional x-ray DACs. In addition, typical culet diameters of 1.5 mm require
~5.5 tonnes to reach 30 GPa, while the 100 GPa measurements required in excess of 10 tonnes.
Figure 9. Evolution of cells used for neutron diffraction. From left to right, the panoramic cell [ref] originally developed
for x-ray spectroscopy; the minibar cell developed specially for the SNAP beamline; the LV-DAC also developed for use
on SNAP, the large cylindrical part houses a membrane driver capable of delivering over 10 tonnes of force.
With such large forces, it was critical to supply radial support to the diamonds. This was done by
copying and enlarging the conical design, first developed for x-ray measurements14. Next, the
seats themselves had to also be supported using steel binding rings, a technology used by
Bridgman in the 1930s that more than doubles the sustainable loads15. Examples of the resulting
designs are given in Figure 10.
Figure 10. Supported diamond anvils used in neutron diffraction experiments. (a) shows a tungsten-carbide-seat (WC),
supported by a steel binding ring (b) shows an equivalent poly-crystalline diamond (PCD) seat. In both assemblies, the
diamonds used have a diameter of 4mm.
As both tungsten carbide and poly-crystalline diamond are extremely hard materials, the seats
must be specially made to provide a sub-micron quality of fit to the diamond cone. Recently,
chemical vapour deposition has made larger (synthetic) anvils available and such anvils may
87
reach sufficient size to allow the use of steel seats, which are much easier to machine and require
less extreme precision.
1.6 Summary and look to the future
While synchrotron x-rays dominate high-pressure crystallography at the present time, very
recent developments look set to expand the remit of research using neutrons. Perhaps the main
driver for this is the substantial government investments made in neutron facilities in the last 10
years. These have lead to two brand new sources (the SNS and the MLF) and upgrades at mature
facilities (such as the second target station at ISIS).
These investments are continue with the European Spallation Source, which is expected to be
the most powerful neutron source ever constructed for research when it begins operations in
2019. With a specified power of 5MW, the ESS will produce the brightest beams in history for
neutron science. Such beams are tailor-made for high pressure and there will be exciting
opportunities to expand the maximum pressure and temperature range. In addition, it will be
possible to explore more challenging diffraction scenarios, such as complex low-symmetry
structure and amorphous, low dimensional and nanomaterial behaviour under pressure.
In addition the new sources, a key parallel technology is that of chemical vapour deposition as a
way to cheaply synthesise large diamonds for anvils. These are already being exploited in new
cell designs that are accessing new regimes of pressure and temperature. This convergence of
technologies even suggests the possibility of a neutron beamline optimised for diamond-anvil
research. While still in the future, the strong scientific drivers for neutron diffraction under
extremes of pressure lend a powerful motivator for such a development.
1.7 Some useful relationships
Following Squires16, these are some useful relationships when calculating neutron properties:
Here, is wavelength (in ), k is wave-vector (in -1), v is neutron velocity (in kms-1), E is
neutron energy (in meV) and T is temperature (in kelvin).
References
Drozdov, A. P., Eremets, M. I. & Troyan, I. A. Conventional superconductivity at 190K at high pressures.
arXiv arXiv:1412.0460 [cond-mat.supr-con] (2014).
Redfern, S. A. T. Neutron powder diffraction of minerals at high pressures and temperatures: some recent
technical developments and scientific applciations. European Journal Minerallogy 14, 251-261 (2002).
Redfern, S. A. T. Neutron powder diffraction studies of order-disorder phase transitions and kinetics.
Neutron Scattering in Earth Sciences 63, 145-170 (2006).
Hastings, J. M. & Corliss, L. M. Neutron Diffraction Study of Manganese Ferrite. Physical Review 104, 328331 (1956).
88
Enderby, J. E., North, D. M. & Egelstaf.Pa. Partial Structure Factors of Liquid Cu-Sn. Philosophical
Magazine 14, 961-& (1966).
Taylor, A. et al. A route to the brightest possible neutron source? Science 315, 1092-1095 (2007).
Guthrie, M. Future directions in high-pressure neutron diffraction. Journal of Physics-Condensed Matter
27 (2015).
Brugger, R. M. We Need More Intense Thermal-Neutron Beams. Physics Today 21, 23-30 (1968).
Guthrie, M. Future directions in high-pressure neutron diffraction. Journal of Physics: Condensed Matter
27, 153201 (2015).
Sears, V. Neutron scattering lengths and cross sections. Neutron news 3, 26-37 (1992).
Klotz, S. Techniques in high pressure neutron scattering (CRC Press, Taylor & Francis Group, Boca Raton,
FL, 2013).
Goncharenko, I. N., Mirebeau, I. & Ochiai, A. Magnetic neutron diffraction under pressures up to 43 GPa.
Study of the EuX and GdX compounds. Hyperfine Interactions 128, 225-244 (2000).
Boehler, R. et al. Large-volume diamond cells for neutron diffraction above 90GPa. High Pressure Research
33, 546-554 (2013).
Boehler, R. & De Hantsetters, K. New anvil designs in diamond anvil cells. High Pres. Res. 24, 391-396
(2004).
Bridgman, P. W. Explorations toward the limit of utilizable pressures. Journal of Applied Physics 12, 461469 (1941).
Squires, G. L. Introduction to the theory of thermal neutron scattering (Cambridge University Press,
Cambridge, 2012).
89
High-Pressure Phase Transitions
High-Pressure
phaseUniversit
transitions
Ross J. Angel, Dipartimento
di Geoscienze,
di Padova, Via G. Gradenigo 6, Padova,
35131, Italy.
Ross J. Angel
email: rossjohnangel@gmail.com
www.rossangel.net
Abstract
Phase transitions are distinguished from reactions by needing only one chemical component in
the Gibbs sense to describe them. Phase transitions are thus, by definition, polymorphic and
occur between phases of the same composition. Many phase transitions that are discovered in
isothermal high-pressure experiments are structural phase transitions. These have the special
property that the space group symmetry of one phase is a sub-group of the symmetry of the
other phase. Consequently, the lower-symmetry phase can be described in terms of a distortion
of the high-symmetry phase, and Landau theory provides the tools to link the measured physical
properties such as cell parameters and elasticity to the structural distortions and the
thermodynamics through the concept of the order parameter.
Keywords
Phase Transitions, Reactions, Spontaneous strain, Elastic softening, Equations of State
Reactions and Phase Transitions
In the absence of phase transitions or reactions, a substance maintains its composition and its
thermodynamic properties of free energy, enthalpy, volume and entropy change smoothly with
changes in the external intensive variables such as pressure and temperature. The same is true
for all of the materials physical properties. In the context of high-pressure measurements, only a
single Equation of State (EoS) is required to describe the P-V-T relationship of a single phase1. In
contrast, phase transitions and reactions involve discontinuous changes in either the enthalpy,
entropy and volume, or in one of the derivatives of the free energy with respect to the intensive
variables.
There is a lot of confused literature as to what distinguishes a phase transition from a reaction2, 3,
in part because of the use of different terminology between the fields of chemistry and physics,
and in part because the idea that the effects of structural phase transitions (which we define
below) can extend very far in P or T from the transition point itself is not widely understood.
The distinction between transitions and reactions is very clear when expressed in terms of the
Gibbs phase rule4, 5 for a closed system: F = N P + C. The Gibbs phase rule defines the degrees
of freedom F within a system in terms of the number of extensive variables N, the number of
phases P, and the number of components C. A phase is a homogeneous material. The
components are the different chemical compositions required to describe all of the phases in the
90
system under consideration. The number of chemical components thus depends on the phases
being considered. Thus, the freezing of H2O water to form water ice involves two phases (P = 2)
but both have the same composition, so C = 1. If we allow both the temperature and pressure to
be varied, then N = 2. The degrees of freedom for this system when both the water and ice are in
equilibrium is thus F = 2-2+1=1. This means that if we use the one degree of freedom to specify a
temperature where ice and water are in equilibrium, the pressure is determined by the
thermodynamics of the system and is not a free variable. Thus the Gibbs phase rule tells us that
there is an equilibrium line in P-T space with F = 1 along which water and ice are in
thermodynamic equilibrium. If only one phase, water, is present without ice, the degrees of
freedom are F = 2, confirming what we know; that liquid water is stable over a continuous range
of P and T.
Now consider a second example. The hydrolysis of water involves the chemical change H2O = H2
+1/2 O2. What is important here is that we now require two chemical components to describe
the system, because we need to describe the H2 and O2 separately. We naturally choose H and O
as the components, although we could legitimately use H2O and H2 and describe the oxygen
phase as being (H2O - H2 ). Whatever choice is made for components, we cannot describe the
hydrolysis of water with just one component. We can now distinguish transitions as requiring
just one component to describe their thermodynamics, from reactions that require more than
one. With this definition phase transitions are always polymorphic; the phases involved in a
phase transition have identical compositions. The freezing of water to form ice is thus a phase
transition, while the hydrolysis of water is a reaction. The phrase phase transformation has
identical meaning to phase transition. Kubickis definition in terms of equivalent vapour phases6
is exactly equivalent to this one.
At equilibrium, at the point of a phase transition, the free energy of the two phases is equal. The
order of a phase transition was first defined by Ehrenfest7 in 1933: In an n-th order phase
transition the n-th and higher derivatives of the Gibbs free energy with respect to intensive
variables such as T and P show discontinuities. Thus, in a first-order transition the derivatives
G P = V and G T = S show jumps. The melting of water ice to water is an example of a
first-order phase transition; the jump in volume and hence increase of density on melting allows
the ice to float on water. In a second-order transition, in the Ehrenfest sense, the volumes and
entropies of the two phases are equal at the transition point, but there are jumps in the second
derivatives of the free energy. Thus, in the context of phase transitions driven by pressure
change, there is no V at the transition, but there is a jump in the compressibility
V P = 2 G P 2 . On increasing pressure, a first-order transition will exhibit a jump in the

volume, while a second-order transition will exhibit a jump in the bulk modulus
K =V P V =V 2 P G 2 . Equivalent definitions of transition order can be used when

the external field is magnetic or electrical and changes in the field drive phase transitions. Since
the time of Ehrenfest, it has become apparent that there are transitions, even in simple
91
materials such as SiO2 quartz, that are intermediate in character between 1st and 2nd order in the
Ehrenfest sense. These can be understood and characterized in the context of Landau theory of
structural phase transitions, which is the main focus of this paper.
Structural Phase Transitions
Landau Theory
The fundamental additional property of a structural phase transition is that it occurs between
two very similar structures, one of which can be considered in some way a distorted version of
the other. The consequence of this distortion is that the distorted structure has a space group
symmetry that is a sub-group of the symmetry of the space group of the undistorted structure.
Thus the melting of water ice to make water is a phase transition (and not a reaction), but is not
a structural phase transition because water has no crystalline symmetry. Structural phase
transitions therefore only occur as transitions between crystalline solids. The symmetry
requirement is the only one for defining a structural phase transition8, 9, 10, so structural phase
transitions can be of any thermodynamic order, can occur by a wide variety of structural
mechanisms and can consequently display a wide range of kinetics ranging from nonquenchable instantaneous transitions to irreversible ones.
A simple example of a structural phase transition which is found in many real perovskite
materials is shown in Figure 1. Consider a layer of octahedra, linked at the corners and free to
rotate about an axis perpendicular to the plane of the diagram. When the rotation angle is zero
the layer of octahedra has square symmetry in two dimensions, with the unit-cell as outlined in
black in Figure 1. If we consider the octahedra to be rigid, then a rotation of one octahedron in
the structure forces all of the other octahedra to rotate by the same amount. Although the
symmetry of the tilted form, in this case, is still square, the unit-cell is approximately doubled in
area (the green square in Figure 1). Therefore the symmetry of the structure has been reduced
because the density of the symmetry elements is less and some symmetry elements, such as the
diad axes on the octahedral corners in the high-symmetry phase, have been lost in the lowsymmetry phase.
Figure 1. The basic concepts of structural phase transitions. Rotation of linked octahedra by an angle breaks the square
symmetry of the un-tilted structure, doubles the area of the unit cell (black to green lines) and reduces the edge-length of
the black square from a0 to a0cos .
92
The central concept in Landau theory is that the degree of distortion of the low-symmetry
structure can be described in terms of an order parameter, often called Q, which is zero in the
undistorted high-symmetry structure, and grows with increasing distortion in the low-symmetry
structure. The amount of structural distortion in the low-symmetry structure is completely
characterized in this example by the rotation angle of the octahedra. The distance between the
centres of the octahedra will be reduced from a0 in the high-symmetry structure to a0cos in the
low-symmetry structure. The structural distortion measured by cos is therefore directly linked
to the change in lattice parameters. Therefore we describe the structural distortion not in terms
of the angle itself, but in terms of an order parameter Q = cos The order parameter Q is
always zero in the high-symmetry phase, and non-zero in the low-symmetry phase. It is often
normalized so that Q = 1 when the structure is fully-ordered, a normalization clear for
transitions involving atomic site ordering, but not so clear for displacive transitions like that in
Figure 1.
The great contribution of Landau theory is to recognize this fundamental link between structural
distortion as measured by the order parameter and the changes in physical properties
accompanying the structural phase transition. Thus, not only are the cell parameters linked to
the structural distortions, but all physical and thermodynamic properties of the low-symmetry
phase can be expressed in terms of the properties of the high-symmetry phase plus the excess
properties arising from the distortions of the structure in the low-symmetry phase. All of these
excess properties, like the cell parameters, scale with the order parameter Q. Some, like the cell
parameters in this example, are proportional to Q. Others, like the area or volume of the unitcell in Figure 1, scale as Q2. The type of this scaling or coupling is determined by the symmetry
changes at the transition, as we will illustrate below. The reason why Landau theory is so
successful in describing the physical and thermodynamic properties of extended systems, and
less so for molecular solids, is also illustrated by Figure 1. Even if the structural units of
octahedra are not completely rigid, provided they are sufficiently stiff they will still transmit the
behaviour of one part of the structure over many unit-cells so that any part of the crystal
structure is influenced by the combined effect of the distortions in other parts of the structure,
even if they are distant. Thus each octahedra responds effectively to the mean field arising from
all distortions in the structure over a length scale much longer than that of 1 or 2 unit cells11, 12, 13
This concept of a mean field is the basis for development of Landau theory8. A complete
description of Landau theory is beyond the scope of this article, where we will focus on the
practical aspects of detecting and characterizing structural phase transitions at high pressures.
Intensity measurements
Figure 1 is an example of a structural phase transition in which the size of the primitive unit cell
changes not just by the factor in cos , but also is approximately doubled (from the black unit cell
in Figure 1 to the green). Changing the size of a unit cell in this way, so that the cell volume of
the lower-symmetry phase is approximately a multiple of the cell of the high-symmetry phase, is
93
termed a zone boundary transition. Because the transition changes the density of lattice points
in real space, it gives rise to additional super-lattice reflections in the diffraction pattern from the
structure. The intensity of these super-lattice reflections is proportional to the square of the
order parameter, and thus the transition can be followed either by measuring the unit-cell
parameters, or by measuring the intensities of the super-lattice reflections.
Structural phase transitions that do not increase the size of the unit-cell are termed zone centre
transitions and only create small numbers of super-lattice reflections if some glide or screw-axis
symmetry is lost in the transition. The terminology arises from the fact that the structural
changes accompanying displacive phase transitions that increase the size of the primitive unit
cell can be described in terms of the condensation (freezing out) of a phonon with a wave-vector
that lies on the Brillouin zone boundary of the high-symmetry phase. In general, all of the
distortions in the low-symmetry phase can be described in terms of distortional waves within the
structure, or normal modes14. These waves have the symmetries of the irreducible
representations (often called irreps) of the space group symmetry of the high-symmetry phase.
The natural description of the distorted low-symmetry structure is then, like the physical
properties, a sum of the high-symmetry average structure plus the distortions represented by the
irreps. The magnitudes of the distortions are the amplitudes of the irreps and thus the order
parameter(s) associated with the transition. Landau theory provides strict symmetry-based rules
for the combination of irreps and their expression in the structure, and thus the number of
possible distorted structures is limited by Landau theory. Structure solution and structure
refinement of the low-symmetry phase is made easier by making use of this concept, because the
irreps reduce problems of correlation in refinement because the symmetry rules reduce the
number of possible structure solutions, and only the mode amplitudes need to be determined10.
This has been especially useful in the determination of the tilting systems in perovskites and
derivative materials14, 15, 16, 17. The interpretation of these refined amplitudes in terms of more
traditional measures of distortion like tilt angles in perovskites18 requires a geometrical analysis19
specific for each structure type. There are a number of on-line tools that can help in
understanding the structural, thermodynamic and symmetry aspects of structural phase
transitions, for example the suite of programs on the Bilbao crystallographic server10, 20, 21 at
http://www.cryst.ehu.es/. Similar analysis tools and software to graphically display the structural
changes induced by individual irreps are provided in the isotropy software suite22 at
http://stokes.byu.edu/iso/isodistort.php.
The concept of spontaneous strain
Any change in the unit-cell parameters of a crystal can be described as a set of strains. In linear
infinitesimal elasticity which is applicable for small changes in lengths, the change in length l
can be described as the strain
= l l 0
in which l0 is the original length1. When the unit-cell
angles are constrained by symmetry to remain unchanged, three linear strains are obviously
sufficient to describe the change in lengths of the three unit-cell edges a, b, and c. For
94
monoclinic and triclinic crystals additional shear strains (1 for monoclinic and 3 for triclinic) are
required to describe the additional changes in unit-cell angles. The resulting six strains formally
constitute a 2nd-rank tensor23. Because the strain tensor is described with respect to Cartesian
axes, the relationship between the tensor strains and the cell parameters depends on the
orientation of the Cartesian axes relative to the crystal axes24, 25, 26. Here we will restrict our
discussion to examples where the unit-cell angles are fixed by symmetry, so we make
11
= a a 0 etc.
As demonstrated in Figure 1, structural phase transitions give rise to changes in cell parameters
that are related to the distortion of the structure. Because these strains arise as a consequence of
the phase transition they are termed spontaneous strains. In this example, the rotation of the
octahedra leads to a doubling of the area of the unit cell, with the true cell parameters of the lowsymmetry phase (green square) being
high-symmetry phase is
2a 0 cos . The equivalent inter-atomic distance in the
2a0 . Therefore the spontaneous strain is
2a0 cos 2a0 =

2a0 cos 1 . Note that value of the strain is the same if we
considered the smaller black square in Figure 1 as the basis for our calculation. Therefore
spontaneous strains do not include the change in cell parameters due to cell-doubling in zoneboundary transitions, but represent the real change in distances within the structures.
Figure 2. Sketch of the possible variation of cell parameters at a continuous structural phase transition from
orthorhombic to tetragonal symmetry. Orthorhombic cell parameters shown by the red lines, tetragonal cell parameters
by blue lines.
95
Figure 2 provides a sketch of how the cell parameters of a crystal might change during a
structural phase transition from tetragonal to orthorhombic symmetry. The total spontaneous
strain in the orthorhombic phase is defined as the strain not from the cell parameters at the
transition point, but relative to the cell parameters that the high-symmetry phase would have
had in the absence of the phase transition. This means that the cell parameters of the highsymmetry phase must be extrapolated to the P and T (or composition X) at which the lowsymmetry cell parameters are measured. This extrapolation is shown in Figure 2 by the blue
dashed lines. It is common to denote the cell parameters of the high-symmetry phase
extrapolated in this way with a subscript, thus a0, c0, V0. The total spontaneous strains in this
11
= a a 0 , 22 = b a0 and 33 = c c0 . We also introduce the concept of the
V V0 and note that, like all strains, V = 11 + 22 + 33 .
volume strain =
V
case are
Cell parameters also change with T and P in a single phase as a result of thermal expansion and
compressibility, without breaking the symmetry of the structure. It is therefore clear that strains
can be non-symmetry-breaking, or symmetry-breaking. It is important to separate these two
types of strains for the analysis of phase, as they can vary with the order parameter in very
different ways. The total strain in any given direction is the sum of the symmetry-breaking (sb)
and non-symmetry breaking (nsb) strains in that direction, for example:
a
a0
11=
=
11, sb + 11,nsb
(1)
For the example in Figure 2, the cell parameters a0, c0, V0 of the tetragonal phase vary without
breaking the symmetry. Therefore the changes in c0 and V0 after the transition do not break the
symmetry and are entirely nsb strains. Similarly the cell parameters a0 = b0 can change in the
tetragonal phase, but these become the independent parameters a and b in the orthorhombic
phase. We therefore conclude that changes in the average of a and b in the orthorhombic phase
are an nsb strain. Using our definition of strains we can now write out all of the nsb strain
components:
(a + b ) 2
11,nsb =
22,nsb =
a0
=
33, nsb
c
1
c0
(2)
11,nsb + 22,nsb + 33,nsb V

The nsb strain tensor has the symmetry of the high-symmetry phase, in this case tetragonal with
=
11,nsb 22 ,nsb 33,nsb . Symmetry rules require that, in a simple phase transition described
by a single order parameter Q, the non-symmetry strains therefore scale in proportion to Q2.
Thus the variation of the nsb strains or the volume strain with P or T indicates how Q2 changes.
Now we turn to the symmetry-breaking (sb) strains. First, no volume strain is symmetrybreaking, so
96
11, sb + 22, sb + 33, sb = 0 . Second, the change in the c-axis length is purely nsb
33, sb = 0 . We therefore conclude that 11, sb = 22 , sb . Therefore the only

(a b ) 2 , which confirms what
symmetry-breaking strains in this case are 11, sb =
22, sb =
a0
we expect; the only change in cell parameters that breaks the tetragonal symmetry is a b in
(equation 2), so
the orthorhombic phase. The symmetry-breaking strains have neither the symmetry of the lowsymmetry phase (e.g. in this case because
phase (in this case because
33,sb = 0 ), nor the symmetry of the high-symmetry
11, sb = 22 , sb ). Instead the sb strain tensor exhibits the symmetry
of the irrep of the high-symmetry phase that is associated with the phase transition25, 27, 28. The
symmetry of the irrep determines whether the sb strains scale with Q or Q2, so a full symmetry
analysis is required to interpret them in terms of order-parameter evolution. Such an analysis
has been performed for the high-pressure tetragonal to orthorhombic transition in stishovite29.
The variation of spontaneous strains
A characteristic of structural phase transitions is that the volume strain is not constant, but
increases continuously as P and T change away from the transition boundary. This is illustrated
in Figure 3 for three different structural phase transitions of different orders. In addition to the
1st- and 2nd-order transitions in the Ehrenfest sense7, Figure 3 includes an example of a tricritical
transition, a class of transitions that is intermediate in properties and emerged from Landau
theory and is quite common. Landau theory and the concept of spontaneous strain allow us to fit
and interpret data such as these.
Figure 3. The variation in unit-cell volumes, volume strain and bulk modulus for three structural phase transitions at
high pressure; first-order transition in spodumene30, tricritical transition in akermanite31 and a 2nd-order transition in
lead phosphate32. The low-symmetry and high-symmetry fields are indicated.
97
For a continuous transition with temperature Landau theory provides a model for the evolution
of the volume strain with temperature in the low-symmetry phase at fixed pressure:
=
V aT Ttr T
(3)
with the transition occurring at a temperature Ttr. The parameter aT is a scaling parameter for
the strain which in principle can be related to other thermodynamic properties such as the
excess entropy and enthalpy arising from the transition. However, values of aT will depend on
the choice of strain definition. Strictly speaking, for consideration of the effects of pressure on
transitions and for large volume changes at transitions, the appropriate definition of finite strain
is expected to be the Eulerian33, 34 strain used in the Birch-Murnaghan EoS1
[(V
V)
2/3
1 / 2 .
However, this leads to considerable algebraic difficulties35. Given that Eulerian finite strains and
Lagrangian infinitesimal strains are approximately linear with one another up to 10% volume
change, it is possible to use the infinitesimal definitions for describing the spontaneous strains
associated with a transition without any loss in the precision of the fit to the data. While the use
of infinitesimal strain may not provide thermodynamically-meaningful values of the parameter
aT, the value of the critical exponent is not sensitive to the strain definition, and its value
indicates the order of transition because the volume strain always couples to Q2. The value of
typically lies between 1/8 and 1, and is a general diagnostic for the type of transition. When
the strain varies linearly with T, and the transition is 2nd-order in character. When
the
transition is termed tricritical. In both cases it is likely that the transition is dominated by a
single process. Other values of can indicate either a first-order transition, that the transition
involves more than one order parameter in the Landau sense, or that some other mechanism is
involved.
The extension of this approach to P-V-T behaviour is easily achieved by defining the variation of
the transition temperature with pressure36. If the phase boundary is a straight line in P-T space,
with a constant slope
=
Ttr Ttr0 + P
dTtr
then the transition temperature at any given pressure P is
dPtr
dTtr
. If the aT and parameters do not change with pressure, it follows that the
dPtr
spontaneous strain at any pressure and temperature is given by:
dT
=
V aT T + P tr T
dPtr
0
tr
(4)
If an experiment is performed at a fixed temperature Texp, then the spontaneous strain as a

function of pressure is:
dT
V = aT tr
dPtr
98
P Ptr
(5)
This is the equation that has been previously used to fit isothermal high-pressure studies of
phase transitions, as shown in Figure 3, with the obvious simplification
V P Ptr . The
derivation emphasises that its use assumes (i) that the phase transition boundary is a straight line
in P-T space, (ii) that the exponent is invariant with P and T, and (iii) that Lagrangian
infinitesimal strains are an appropriate measure of the spontaneous strain. There is also the
additional assumption that the transition behaviour either involves a single order parameter, or
is dominated by one. In some cases in which strong renormalisation of the phase transition
occurs with pressure (e.g. in lead phosphate32), the critical exponent varies across P-T space,
and the simplified approach developed here cannot be applied to both high-pressure and hightemperature experiments, even though it can be used to fit the high-pressure data displayed in
Figure 3. This extension of the conventional Landau approach from T-driven transitions to high
pressures and the consequent interpretation of the value of as indicating the thermodynamic
order of the transition strictly only works for small spontaneous strains and close to the phase
transition but appears in practice to yield correct results37.
Elastic softening
dP
. The elastic
dV T
The isothermal bulk modulus of a material defines its stiffness: K =

V
T
behaviour of a material undergoing a phase transition therefore follows from the differentiation
of the expression of the volume V = V 0 (1 + V ) , thus37:
d( + )
dV dV0
(1 + V ) + V0 1 V
=
dP
dP
dP
(6)
Which, by some re-arrangement and introduction of the bulk modulus of the high-symmetry
phase K0, yields an expression for the bulk modulus of the low-symmetry phase:
1
1
d V
1
K 0
=
(1 + V ) dP
K
V
( 1) Ttr
With: =
aT P Ptr
P
Ptr
(7)
Care must be taken with respect to the signs of derivatives; when the low-symmetry phase is the
high-temperature phase,
V
has the same value, but opposite sign. Equation (7) shows that
P
the bulk modulus and spontaneous strain are two intimately-linked physical properties of a
material under-going a phase transition, and the consequences are displayed in Figure 3.
For a second-order transition studied at high pressures, = 1 and thus
while
V P Ptr
V
is a constant. Thus equation (7) shows that there is no significant softening prior to
P
99
the transition, and the transition point itself is marked by a jump in the bulk modulus because it
is related to the 2nd-derivative of the free energy with respect to pressure7.
For 1st-order and transitions intermediate in order between 1st and 2nd-order, equation (7) shows
that there is elastic softening. As the phase transition is approached from the low-symmetry side
the spontaneous strain decreases to zero so the term
1
becomes equal to 1. But, at the
(1 + V )
same time P Ptr tends towards zero, which means

because
( 1) < 0 . Thus
P Ptr
( 1)
becomes very large
V
increases rapidly and dominates the bulk modulus of the lowP
symmetry phase, which is softened as the transition is approached (Figure 3).

The type of elastic softening that can be measured in the vicinity of a structural phase transition
depends on the timescale and nature of the experimental measurement. In an isothermal
compression experiment in which the unit-cell parameters are measured at high pressures by
diffraction, the timescale is long because the order parameter Q responds to the pressure change,
and the equlibrium values of Q and
V are measured at each pressure step. In this case equation
(7) describes the softening. On the other hand, if elastic measurements are made by
spectroscopic methods, the timescale is fast, and the measured elastic moduli will reflect the
response of the material to small imposed stresses at constant Q, in which case the elastic
response is not given by equation (7) but instead by the susceptability of the crystal38.
Experimental measurements
First-order structural phase transitions are marked by a step in the unit-cell volume and are thus
easy to detect immediately from plots of the volume and cell parameters against pressure. If the
volume step is large, then the properties of the low-symmetry phase are dominated by the jump
in the properties at the transition, so the EoS and the other properties of the two phases can
often be analysed separately although the low-symmetry phase may have strange values of the
pressure derivative of the bulk modulus as a consequence of the pre-transition softening39. For
non-first-order (i.e. continuous) transitions, there is no step in volume at the transition, and the
transition may not be obvious even after extensive data analysis. One analytical tool that often
reveals a continuous phase transition is the f-F plot of the P-V data40, 41 which has revealed highpressure transitions in materials as diverse as lawsonite42 and ferro-relaxor perovskites43. Once
the transition has been detected, the order of the transition can be determined immediately from
analysis of the spontaneous volume strain to determine the critical exponent . This can be
performed by extrapolation of the cell-parameters of the high-symmetry phase to the pressures
at which the low-symmetry phase had been measured, followed by calculation of the
spontaneous strain components, and their subsequent fitting44. This has the disadvantage of
being a step-wise process during which error propagation from the data into the final fitting of
the strain variation with pressure is difficult. A simpler and more robust approach is to fit the
100
cell parameters of both phase simultaneously with the EoS of the high-symmetry phase plus a
Landau-type expression (equation 5) for the spontaneous strain. This has been implemented in
EosFit for both P-V, P-V-T, and V-T fitting45.
Conclusions
Landau theory is a very powerful approach to the characterization and analysis of high-pressure
structural phase transitions because it provides the theoretical link between different measurable
physical properties, the symmetry changes, and the structural changes accompanying the
transition. From one side, this means that the essential thermodynamics of a structural phase
transition can be determined by a single type of measurement. Thus, the evolution of volume
spontaneous strain at a transition is intimately connected to the elastic softening, and a
measurement of either reveals the nature of the transition (Figure 3). From the other side, the
theory can be used to test whether different kinds of measurements are consistent with one
another. An early experimental example was the study of ReO3 in which the corner-linked ReO6
octahedra tilt, rather like Figure 1. A neutron powder diffraction study46 showed that octahedra
remained essentially rigid in the low-symmetry phase, and that the tilt angle evolved in
proportion to (P Pc )
0.322 (5 )
(P Pc )
23
while the excess volume associated with the transition evolves as
, thus providing an experimental confirmation of the general relation-ship
V Q .
2
However, Landau theory is not always a useful tool for characterising high-pressure structural
phase transitions. There are many high-pressure phase transitions in which the symmetry of one
phase is the same, or a sub-group, of the other, but in which the structural changes are
sufficiently great that the transition is strongly first order in character, and the properties of the
low-symmetry phase are dominated by the changes at the transition and evolve only slightly with
distance from the phase transition. Examples include structural re-arrangements in MOFs47, 48
involving bond-breaking and reformation, and discontinuous changes in bonded coordination to
cation centres in frameworks49.
Acknowledgments
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Salje EKH. Application of Landau Theory for the Analysis of Phase- Transitions in Minerals. Physics
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Crystallographica A 58, 66-71 (2002).
Howard CJ, Stokes HT. Group-theoretical analysis of octahedral tilting in perovskites. Acta
Crystallographica Section B-Structural Science 54, 782-789 (1998).
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(1972).
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structures. Acta Crystallographica B 67, 302-314 (2011).
Aroyo MI, Kirov A, Capillas C, Perez-Mato JM, Wondratschek H. Bilbao crystallographic server. II.
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properties for phase transitions in minerals. European Journal of Mineralogy 10, 621-691 (1998).
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plagioclase feldspars from thermal expansion measurements. American Mineralogist 96, 992-1002 (2011).
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in Minerals (ed^(eds) (2000).
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ZnSiO3. Physics and Chemistry of Minerals 27, 719-731 (2000).
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(2004).
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pressure-induced phase transitions in ReO3. Physical Review B 33, 4793-4798 (1986).
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rearrangement in a zinc imidazolate framework: a high-pressure single-crystal X-ray diffraction study.
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photoluminescence properties of a terbium-adipate framework. Journal of Solid State Chemistry 202, 99104 (2013).
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104
Understanding phase stability: intermolecular interactions in molecular crystals
Understanding
phaseofstability:
interactions
inConditions, The
Simon
Parsons, School
Chemistryintermolecular
and Centre for Science
at Extreme
molecularofcrystals
University
Edinburgh, Kings Buildings, West Mains Road, Edinburgh, Scotland. EH9 3FJ
S.Parsons@ed.ac.uk
Simon Parsons
http://www.cryst.chem.ec.ac.uk
School of Chemistry and Centre for Science at Extreme Conditions, The Univ. of
Edinburgh, Edinburgh, UK
S.Parsons@ed.ac.uk
www.cryst.chem.ec.ac.uk
Abstract
Methods for estimating free energy differences for different crystalline forms of molecular
crystals are described, enabling quantification of the contributions of volume, internal energy,
zero point energy, thermal effects and entropy to be estimated, providing insight into the factors
which promote stability under different conditions. Internal energies can be evaluated with the
semi-empirical PIXEL method, which provides a break-down of total energies into moleculemolecule energies, further subdivided into electrostatic, polarisation, dispersion and repulsion
effects. Thermal effects can be addressed using vibrational frequency data calculated using
periodic density functional theory. Though volume minimisation is the dominating
thermodynamic driving force in many high-pressure phase transitions, in some, particularly
below 1 GPa, entropy or internal energy effect may also be important.
Keywords
Intermolecular interactions; PIXEL method; Internal energy; entropy; free energy.

1. Introduction
Understanding and prediction of phase transitions and polymorphism1 in the molecular solids is
one of Chemistrys big questions, and the aim of this Chapter is to outline some methods which
can be used to analyse the thermodynamic factors which drive phase transitions and lead to
polymorphism. Such quantitative analysis provides physical insight into the reasons that the
preferred structural form of a material varies with conditions.
A phase transition is thermodynamically allowed if, under a given set of conditions of
temperature (T) and pressure (p), its associated Gibbs free energy change, G, is negative.2 G
can be broken-down into component terms according to Equ. 1.
G = U + pV TS
(1)
In this equation U represents the internal energy. This term contains contributions from
intermolecular interactions such as hydrogen bonds. It may also contain intramolecular terms if,
for example, a change in molecular conformation occurs over the course of a transition. The
zero point energy and thermal energy also contribute to U, the latter increasing as higher
vibrational energy levels become occupied with increasing temperature. V is the volume, and
the term pV reflects the drive to fill space efficiently as pressure increases. S is entropy, which
in a solid is a measure of the number of accessible vibrational states: materials with very low
105
frequency vibrations have a higher entropy. Disorder may add an additional conformational
entropy term.
The following sections will describe some practical methods for estimating each of these terms
starting from structural data alone. The methods described are those that the author has found
most useful in work on phase transitions in molecular materials at pressures up to about 10 GPa.
No attempt is made to survey all possible methods, and indeed, different authors would certainly
select a quite different set of methods.
2. The volume term
The pV term is the simplest to calculate. Suppose phase I of a material undergoes a phase
transition to phase II at a pressure p. Phase I has a unit cell volume VI with ZI molecules per unit
cell; equivalent quantities VII and ZII can be defined for phase II. The molecular volumes of
phases I and II are VI/ZI and VII/ZII, respectively. If p is in GPa and the cell volumes in 3, then
pV in kJmol1 is given by
V
V
6.023 1023.109 VII VI
p
~ 0.6 p II I
30
3
10 .10
Z II Z I
Z II Z I
(2)
where the factors 109, 1030 and 103 convert from GPa to Pa, 3 to m3 and J to kJ, respectively;
Avogradros number gives the value per mole.
Example: The crystal structure of methyl 2-(carbazol-9-yl)benzoate3 forms in Pn in a phase (I)
with eight molecules per asymmetric unit (Z = 16) under ambient conditions. Between 4.9 and
5.3 GPa the material undergoes a phase transition to a phase-II with two molecules in the
asymmetric unit in space group P212121 (Z = 8); the molecular volume (V/Z) is plotted against
pressure in Fig. 1.
In order to assess the influence of volume on the thermodynamics of the transition the phases
need to be compared at a single selected pressure. The unit cell volume of phase II at 5.3 GPa
was measured to be 2399.2 3 by single crystal X-ray diffraction, and so the molecular volume at
this pressure = 2399.2/8 = 299.9 3. There are no data for the volume of phase I at 5.3 GPa, so it
is necessary to extrapolate the volume versus pressure curve measured at lower pressures using
an equation of state, or perhaps by eye. The estimated molecular volume in phase I at 5.3 GPa
is 307.0 3. Using these values in Equ. 2 give
pV =
0.6 5.3 GPa (299.9 307.0) 3
= 22.6 kJmol-1
The lattice energies of polymorphs at ambient pressure usually differ by 10 kJmol1 or less, often
much less, and so a contributing term of ~23 kJmol1 has a substantial stabilising influence on
phase II. High-pressure phase transitions are usually driven by the need to fill space efficiently,
an idea which is encapsulated in the pV term.
106
Figure 1. Variation of molecular volume with pressure in methyl 2-(carbazol-9-yl)benzoate.
At ambient pressure the pV term can usually be neglected. For two phases differing in
molecular volume by (an unusually large) 7 3 at ambient pressure (104 GPa) the pV
contribution is only 0.42 Jmol1 (note J not kJ).
3. The internal energy
3.1 Preamble
Analysis of the terms which contribute to the internal energy of a crystal structure not only
provides insight into the thermodynamics of alternative solid forms, it is also a systematic
method for interpretation of crystal structures. The thermodynamic stability of a crystal
structure is often rationalised by analysis of structure-directing, intermolecular atom-atom
contacts such as hydrogen bonds, halogen bonds and -stacking.4 The simplicity of this
approach is very appealing, but stability is a thermodynamic concept which depends on relative
energies, and so in distance-based analysis it is necessary to assume that short inter-atomic
contacts are evidence of stabilising intermolecular interactions. Under some circumstances this
assumption may either not be correct, or may obscure a more complex picture.5, 6 Calculation of
accurate intermolecular interaction energies from crystal structure data is now routinely possible
using empirical atom-atom potentials, semi-empirical approaches such as the PIXEL7 or qGRID8
methods, or using quantum mechanical methods including ab initio calculations or symmetryadapted perturbation theory (SAPT)9 or hybrid approaches such as that recently described by
Spackman and co-workers which makes use of rapid quantum mechanical calculations scaled to
reproduce energies of higher level methods.10
3.2. The PIXEL method for calculating intermolecular interaction energies
In the following paragraphs the PIXEL method7 will be described in some detail in part because
it forms the subject of a workshop later in this School, but also because it has proved to be a
particularly effective method for the analysis of molecular crystal structures both at ambient and
at elevated pressures. The PIXEL method is a semi-empirical technique devised by Gavezzotti7
for evaluating intermolecular interactions based on integrations over electron densities of
molecules. Energetic analysis of molecular crystal structures can be carried out quickly with an
107
accuracy comparable to quantum mechanical methods.11, 12 PIXEL calculations can be

accomplished with the freely-available CLP package, down-loadable from
http://www.angelogavezzotti.it/Public/main.htm.13
PIXEL calculations yield the total lattice energy partitioned into individual molecule-molecule
energies, which are themselves partitioned into four terms: Coulombic, polarisation, dispersion
and repulsion.14 The separation of contributions allows for the character of individual
interactions and overall crystal packing to be inferred from the dominant terms, providing
chemical insight. The PIXEL method requires definition of certain atomic parameters, but these
are mostly physical quantities, and one of the most appealing features of the method is the
transferability of parameters across many different chemical systems, including organic and
organometallic crystals structures.
In a PIXEL analysis the electron density in an isolated molecule is first calculated using a
quantum mechanical package such as GAUSSIAN09. Electron densities are obtained in singlepoint calculation (i.e. without geometry optimisation) in the crystal-structure geometry. The
only necessary modification, applicable to X-ray crystal structures, is to extend X-H distances to
correct for the effects of the asphericity of H-atom electron densities. Calculations are typically
at the MP2 or DFT-B3LYP level with a 6-31G** basis set. Note that an approximation made in
the subsequent calculations is that the calculated electron density is unperturbed by its
environment in the crystal.
The electron density model is generated in a cube format file, consisting of a grid of blocks of
electron density or pixels. The charge of the kth pixel, Qk, is kVk where k is the electron density
and Vk the volume of the pixel. Typically the step-size of the grid is 0.08 , and even for a small
molecule such as the amino acid alanine, this representation consists of almost 1.5 million pixels.
In order to speed up subsequent energy calculations, blocks of n x n x n pixels are condensed into
superpixels; n is called the condensation level and is usually between 3 and 5. If the charge
associated with a pixel is below a certain threshold (typically 106 e), the charge is set to zero and
the overall molecular charge re-set; this procedure also saves overall computation time.
The charge distribution in the crystal structure can be represented by condensed grids of
electron density, along with the associated nuclear density, distributed using the space group
symmetry. A cluster of molecules extending to a user-selected radius is generated about a central
reference molecule; typically the radius is between 10 and 20 , encapsulating a few hundred
molecules. The electrostatic, polarisation, dispersion and repulsion energies are then evaluated
between the reference molecule and each molecule within the cluster.
Evaluation of the electrostatic interaction energy between two molecules is shown schematically
in Fig. 2. Since the charges Q1 in the reference molecule and Q4 in a symmetry-equivalent are
known along with the distance (r14) between them, the electrostatic energy between these two
pixels is given by Coulombs Law,
Eelec =
108
Q1Q4
4 o r14
(3)
where 0 is the permittivity of free space. The total electrostatic energy between the two
molecules is the sum of terms for all pixel-pixel, pixel-nucleus and nucleus-nucleus pairs. The
electrostatic contribution to the lattice energy is obtained by summing the contributions from
the reference molecule to all other molecules in the cluster. A collision avoidance procedure is
invoked in cases where pixels overlap.
Figure 2. Schematic representation of the evaluation of energy terms in the PIXEL method. [Original figure by R.D.L.
Johnstone]
Evaluation of polarisation, dispersion and repulsion follows a similar pixel-by-pixel evaluation of

molecule-molecule energies. Full details are available in ref. 7.
3.3 Performance and limitations of the PIXEL method
The lattice energies calculated using the PIXEL method have been compared to experimentallydetermined sublimation enthalpies for 172 organic crystal structures (Fig. 3a).14 A least-squares
fit had a gradient of 0.96 with a correlation coefficient (R2) equal to 0.79. A study for 43
compounds containing transition metals had a gradient of 0.99 with R2 = 0.85 (Fig. 3a).15 A
similar level of agreement exists between individual dimer energies calculated with PIXEL and
DFT for 60 different dimers,16 and between PIXEL and SAPT2+3 energies for the S22 database of
intermolecular interaction pairs (Fig. 3b).
Figure 3. (a) Comparison of PIXEL lattice energies and experimental sublimation energies for organic compounds (blue
squares) and transition metal complexes (red circles). Data for the former were kindly provided by Professor Angelo
Gavezzotti. (b) Comparison of PIXEL and SAPT2+3 energies for molecular dimers in the S22 database [S.Parsons,
unpublished data]. The lines in both cases are y = x.
109
The accuracy of PIXEL calculations, the break-down of the total lattice energy into individual
molecule-molecule energies which are themselves partitioned into readily understandable terms,
and the speed of the calculations even on ordinary desk-top computers make them extremely
attractive in structure interpretation and thermodynamic modelling. Nevertheless, it is
important to recognise certain limitations of the PIXEL method. It assumes that an interaction
is non-covalent, and it cannot be applied to cases of partial bond formation or other situations
involving electron-sharing for which full quantum mechanical treatments are necessary. Ab
initio calculations of dimer energies represent an alternative approach, but the total energy is not
broken-down into contributing terms. At the highest level symmetry-adapted perturbation
theory (e.g. SAPT2+3) is as accurate as methods such as CCSD(T),17 and it does yield energies
partitioned into component electrostatic, polarisation (induction), dispersion and repulsion
(exchange) terms. It is quite time-consuming, though lower-levels of SAPT (e.g. SAPT0) can also
perform well, benefiting from error cancellation.9 SAPT calculations can be carried out with the
freely-available and user-friendly PSI-4 code.18
The PIXEL method addresses intermolecular interactions, and so energy differences arising from
different intramolecular geometry need to be calculated separately when comparing different
phases. For example, amino acids are zwitterionic in the solid state, but neutral in the gas phase
as the result transfer of H+ from the amino to the acid group. While an experimental sublimation
energy determination would reflect the proton transfer energy, the result of a PIXEL calculation
would correspond to formation of gas phase zwitterions. The proton transfer energy would need
to be calculated in a separate step, for example by ab initio methods, and added to the calculated
lattice energy to obtain a quantity comparable to an experimental sublimation energy.
Figure 4. (a) Destabilising hydrogen-bonded dimer in -glycine. (b) The same dimer depicted using Hirshfeld surfaces
coloured according to electrostatic potential (range -0.005 au (red) to +0.005 au (blue).
Finally, it is important to remember that the PIXEL method calculates molecule- molecule
energies; the same is true of ab initio and SAPT calculations. If two molecules are connected by
a prominent atom-atom interaction, such as a hydrogen bond, it is tempting, but wrong, to
equate with molecule-molecule energy with the atom-atom interaction energy. The fallacy can
be illustrated by the interaction shown in Fig. 4 present in the crystal structure of the
polymorph of glycine.19 The interaction is characterised by a short NHO hydrogen bond, but
the overall molecule-molecule energy is destabilising (+18 kJ mol1) as the result of unfavourable
juxtaposition of positively charged regions of the two molecules. This example also shows how
110
focussing only on a few notable interatomic interactions can give a misleading impression of the
factors which promote thermodynamic stability in a crystal structure.
3.5 Visualisation of intermolecular interactions
Graphical tools are essential for interpreting and understanding the results of energy
calculations. Intermolecular interactions can be depicted using structural visualisation software
such as Mercury,20 Diamond21 or CrystalMaker,22 which all have facilities for selection and
editing of interactions (Fig. 4a); Mercury has powerful structure comparison facilities which
enable the similarity of different phases to be assessed quickly. Tools based on Hirshfeld surface
analysis,23, 24 available in the CrystalExplorer software,25 such as finger-print plots and surfaces
encoded with different properties such as measures of atom-atom distances or topology are also
designed to enable rapid analysis of structural features. Use of Hirshfeld surfaces coloured
according to the electrostatic potential (Fig. 4b) are especially valuable for visualising
electrostatic interactions: this is important because interaction geometry is often determined by
electrostatics, even in cases where dispersion is the dominant term.26
Exhaustive analysis of intermolecular geometric parameters can be accomplished with
PLATON.27 Note, however, that PLATON estimates standard uncertainties (s.u.s) by
propagation of the s.u.s of the fractional atomic coordinates and cell parameters which are
present in a cif, and recalculation of selected parameters using the full least-squares inverse
normal matrix available to refinement programs is recommended.
3.6 Zero-point energy and vibrational enthalpy
The zero point energy (ZPE) is associated with occupation of the lowest vibrational energy levels,
and has a finite value even at absolute zero. It can be estimated in the harmonic approximation
from a vibrational frequency calculation (see below) using
ZPE =
1 n
h i
2 i =1
(4)
where i are the vibrational frequencies, h is Planks constant and the sum runs over all n
vibrational modes. The largest contributors to the zero point energy are high-frequency
vibrations, such as stretches and bends involving intramolecular N-H and O-H bonds. Hydrogen
bonding influences these frequencies, and so ZPE differences between different phases may be of
the order of a few kJmol1, i.e. significant in the context of typical total polymorph lattice energy
differences. For example the ZPE difference between and glycine28 has been estimated to
differ by almost 2 kJmol1, compared to an overall enthalpy difference of 0.3 kJmol1.
The vibrational enthalpy (Hvib) arises because vibrational energy levels above the ground state
become populated as temperature increases, and this factor can also be estimated from
harmonic frequencies using
n
H vib =
i =1
h i exp(h i / 2kT )
1 exp(h i / 2kT )
(5)
111
where k is Boltzmanns constant and T is temperature. Low frequency modes contribute most to
Hvib, and so this term can also contribute significantly to polymorph differences, approximately 1
kJmol1 in the case of and glycine.28
Figure 5. Phonon spectra of theophylline form-I (CSD refcode BAPLOT04, top) and form-II (BAPLOT06, bottom).
Notice that the modes are more concentrated towards low frequency in form-I. Figure from ref. 29
4. Entropy
The ZPE, vibrational enthalpy and the entropy of a crystalline solid all depend on vibrational
frequencies. These are obtained using a force-field or quantum mechanical approach in which
the geometry of the crystal structure is first optimised, and the frequencies then calculated by
taking the second derivative of the energy with respect to atomic displacements in the x, y and z
directions. The vibrational entropy, Svib, is given by
Svib
1 n h i exp(h i / 2kT )
k ln[1 exp(h i / 2kT )]
T i =1 1 exp(h i / 2kT )
(6)
Practical calculations usually apply the harmonic approximation, and should ideally include the
effects of phonon dispersion, accounting for acoustic as well as optical modes.
Entropy increases as access to energy levels is promoted by increasing temperature. Lowfrequency vibrational modes have the most influence, and since these vary considerably between
alternative phases, entropy is an important factor influencing phase stability. For example two
phases of the pharmaceutical compound theophylline are known.29 Form-II is
thermodynamically stable at low temperature on account of its more favourable lattice energy,
but form I has more low-frequency modes in its phonon spectrum, giving it an entropy
advantage of 6.5 Jmol1K1. Form-II therefore transforms to form-I at high temperature,
illustrating the idea of enthapy-entropy compensation, where a looser structure with weaker
intermolecular interactions can be stabilised by its higher entropy.14
112
5. Case Study: Salicylamide30

Salicylamide crystallises at ambient pressure in phase-I. A crystal was loaded into a diamond
anvil cell and diffraction data collected at ambient pressure, 0.3 GPa and then in stages up to 5.1
GPa; no phase changes were detected. However, a different phase (II) was obtained when
salicylamide was crystallised from 4:1 MeOH/EtOH at 0.2 GPa. Hirshfeld fingerprint plots (Fig.
6) show that both structures contain hydrogen bonds, as would be expected, but that phase-I has
closer HH contacts (indicated by the skirt of points between the two spikes), and is less
efficiently packed (the diffusely distributed points at long distances).
Figure 6. Hirshfeld fingerprint plots for (a) salicylaldoxime-I and (b) salicylaldoxime-II.
Volume: Phase-II is denser than phase-I, with a volume of 154.7 3 per molecule at 0.2 GPa,
compared to 163.3 3 per molecule for phase-I, a value interpolated from the volumes at ambient
pressure and 0.3 GPa. For a putative transition phase I phase II at 0.2 GPa, the molecular
volume difference is 8.6 3, equating to a pV term of 1 kJmol1, favouring phase-II.
Electrostatic
Polarisation
Dispersion
Repulsion
Total
Phase-I
87.4
32.1
87.0
+104.8
101.7
Phase-II
63.8
24.6
99.0
+88.5
98.9
Table 1. Contributions to the lattice energies of salicylaldoxime phases I and II. Values calculated using PIXEL, all
energies are in kJmol1.
Lattice energy: Table 1 shows the results of PIXEL calculations for the two phases. The values
quoted for phase-II were determined directly from the coordinates determined at 0.2 GPa; those
for phase-I are interpolated to 0.2 GPa from the parameters measured at ambient pressure and
0.3 GPa. The electrostatic interactions in phase-I are substantially stronger than those in phaseII, a feature that can be related to the more linear NHO bond angles in phase-I (175 and 164
in phase-I and 146 and 157 in phase-II).31 Part of the electrostatic energy deficit in phase-II is
made up by dispersion interactions, including -stacking and CH contacts which are both
more numerous and more energetic than in phase-I. The longer HH contacts in phase-II are
mirrored in the lower repulsion energy. Nevertheless, the data in Table 1 show that the lattice
energy component of the free energy favours phase-I by 2.8 kJmol1.
113
Zero point energy and vibrational enthalpy: Vibrational frequencies of phases I and II were
calculated using periodic DFT and used to estimate the vibrational contributions to the
thermodynamic functions at 298.15 K. The results show that ZPE(III) is 1.1 kJmol1, that is
phase-II has a smaller ZPE than phase-I. Break-down of the contributions to the zero-point
energy in the manner described by Hudson28 shows that the ZPE difference can be traced to
lower vibrational frequencies of phase-II in the regions from 1000-1200 and 1600-1800 cm1,
which contain rocking and bending modes centred on the NH2 groups. As Hudson has observed
in glycine, these modes are higher in frequency in phase-I because they lead to deformations of
H-bonds which are more linear (and energetic) than in phase-II. OH stretching is also higher
frequency in phase-I, though this is somewhat counter-intuitive as the stronger H-bonding in
this phase would normally be associated with a frequency reduction.
Hvib(III) = +0.8 kJmol1, as a result of differences in the frequency of lattice vibrations in the 0
400 cm1 region. These modes are lower in frequency in phase-II because H-bonding is
weaker, and therefore become populated at a lower temperature than equivalent modes in
phase-I.
Entropy: Entropic contributions drop-off quite rapidly with frequency, and the same effect
described above in the context of Hvib means that phase-II is also favoured by entropy.
TS(III) is 4.1 kJmol1 at 298.15 K.
The overall free energy balance sheet is shown in Table 2. The formation of salicylamide-II at
0.2 GPa can be understood in terms of (a) the replacement of H-bonds by dispersion-dominated
stacking and CH interactions; (b) its higher density and (c) its lower vibrational frequencies.
The last of these occurs because of weaker H-bonding in phase-II which, paradoxically perhaps,
gives this polymorph an advantage in both zero point energy and entropy.
Phase-I Phase-II
Energy
(Lattice energy)
+2.8
pV
1.0
TS
4.1
ZPE
1.1
Hvib
+0.8
Total G
2.6
Table 2. Terms contributing to G(III) for salicylamide. Values in kJmol1.
Acknowledgements
Many of the results described in this Chapter were obtained by Peter Wood, Russell Johnstone
and Andrew Maloney over the course of their PhD research at The University of Edinburgh. We
are grateful for financial support by The Cambridge Crystallographic Data Centre and the
Engineering and Physical Sciences Research Council, for allocations of synchrotron beam-time
at SRS, Daresbury Laboratory, Diamond Light Source and ISIS, and for support and advice by
114
The Eastchem Research Computing Facility. We also thank Professor Angelo Gavezzotti for his
constant interest and advice over the course our work.
References
1. J. Bernstein, Polymorphism in Molecular Crystals OUP, Oxford, 2008.

2. M. T. Dove, Structure And Dynamics: An Atomic View of Materials, OUP, Oxford, 2001.
3. R. D. L. Johnstone, M. Ieva, A. R. Lennie, H. McNab, E. Pidcock, J. E. Warren and S. Parsons,
CrystEngComm, 2010, 12, 2520-2523.
4. T. S. Thakur, R. Dubey and G. R. Desiraju, IUCrJ, 2015, 2, 159-160.

5. J. Dunitz, IUCrJ, 2015, 2, 157-158.
6. J. D. Dunitz, A. Gavezzotti and S. Rizzato, Cryst. Growth Des., 2014, 14, 357-366.
7. A. Gavezzotti, Z. Kristallogr., 2005, 220, 499-510.
8. N. J. J. de Klerk, J. A. van den Ende, R. Bylsma, P. Grancic, G. A. de Wijs, H. M. Cuppen and H. Meekes,
Cryst. Growth Des., 2016, 16, 662-671.
9. E. G. Hohenstein and C. D. Sherrill, Wiley Interdiscip. Rev. Comput. Mol. Sci., 2012, 2, 304-326.
10. M. J. Turner, S. Grabowsky, D. Jayatilaka and M. A. Spackman, J. Phys. Chem. Lett., 2014, 5, 4249-4255.
11. L. Maschio, B. Civalleri, P. Ugliengo and A. Gavezzotti, Journal of Physical Chemistry A, 2011, 115,
11179-11186.
12. W. B. Schweizer and J. D. Dunitz, Journal of Chemical Theory and Computation, 2006, 2, 288-291.
13. A. Gavezzotti, New J. Chem., 2011, 35, 1360-1368.
14. A. Gavezzotti, Molecular Aggregation - Structure Analysis and Molecular Simulation of Crystals and
Liquids, Oxford University Press, New York, 1st edn., 2007.
15. A. G. P. Maloney, P. A. Wood and S. Parsons, CrystEngComm, 2015, 17, 9300-9310.
16. L. Maschio, B. Civalleri, P. Ugliengo and A. Gavezzotti, J. Phys. Chem. A, 2011, 115, 11179-11186.
17. J. C. Flick, D. Kosenkov, E. G. Hohenstein, C. D. Sherrill and L. V. Slipchenko, J. Chem. Theory Comput.,
2012, 8, 2835-2843.
18. J. M. Turney, A. C. Simmonett, R. M. Parrish, E. G. Hohenstein, F. A. Evangelista, J. T. Fermann, B. J.

Mintz, L. A. Burns, J. J. Wilke, M. L. Abrams, N. J. Russ, M. L. Leininger, C. L. Janssen, E. T. Seidl, W. D.
Allen, H. F. Schaefer, R. A. King, E. F. Valeev, C. D. Sherrill and T. D. Crawford, Wiley Interdisciplinary
Reviews: Computational Molecular Science, 2012, 2, 556-565.
19. S. A. Moggach, W. G. Marshall, D. M. Rogers and S. Parsons, CrystEngComm, 2015, 17, 5315-5328.
20. C. F. Macrae, I. J. Bruno, J. A. Chisholm, P. R. Edgington, P. McCabe, E. Pidcock, L. Rodriguez-Monge,
R. Taylor, J. van de Streek and P. A. Wood, J. Appl. Cryst., 2008, 41, 466-470.
21. CrystalImpact, Crystal Impact GbR, Postfach 1251, 53002, Bonn, Germany, Bonn, Germany, 2004.
22. CrystalMaker Software Ltd, Oxford, England (www.crystalmaker.com).
23. J. J. McKinnon, M. A. Spackman and A. S. Mitchell, Acta Cryst., 2004, B60, 627-668.
24. M. A. Spackman and D. Jayatilaka, CrystEngComm, 2009, 11, 19-32.
25. S. K. Wolff, D. J. Grimwood, J. J. McKinnon, M. J. Turner, D. Jayatilaka and M. A. Spackman, University

of Western Australia, 2012.
26. M. A. Spackman, J. J. McKinnon and D. Jayatilaka, CrystEngComm, 2008, 10, 377-388.
27. A. L. Spek, J. Appl. Cryst., 2003, 36, 7-13.
115
28. S. A. Rivera, D. G. Allis and B. S. Hudson, Cryst. Growth Des., 2008, 8, 3905-3907.
29. J. Nyman and G. M. Day, CrystEngComm, 2015, 17, 5154-5165.
30. R. D. L. Johnstone, A. R. Lennie, S. F. Parker, S. Parsons, E. Pidcock, P. R. Richardson, J. E. Warren and

P. A. Wood, CrystEngComm, 2010, 12, 1065-1078.
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116
Principles of Intensity Data Reduction
Principles
of Dipartimento
intensity data
reduction Universit di Padova, Via G. Gradenigo 6, Padova,
Ross
J. Angel,
di Geoscienze,
35131, Italy.
Ross J.rossjohnangel@gmail.com
Angel
email:

www.rossangel.net
Abstract
The determination of the structure of a crystalline material at high pressures is dependent upon
the accurate measurement of the intensities of X-ray or neutron beams diffracted by the sample,
and the precise correction of the intensities for the various effects of the high-pressure device. In
this contribution the methods required to obtain accurate structure refinements from highpressure single-crystal X-ray diffraction measurements are outlined.
Keywords
Intensity Measurement, Single-crystal, Data Reduction, Absorption, Structure Refinement
Introduction
Diffraction gives us two fundamentally different types of information. The positions of the
diffracted beams tell us, through the Bragg equation, the unit-cell parameters of the crystal but
nothing (except in the simplest structures) about the configuration of the atoms or the distances
between them. In the vast majority of crystal structures the atoms occupy positions within the
unit cell that are not fixed by symmetry. The atom positions, and thus the bond-lengths and
angles within the crystal structure, can only be determined from the intensities of the diffracted
beams. The intensity of the diffracted beam or reflection indexed as H = hkl is represented by the
structure factor equation:
F ( hkl ) =
B j sin 2
f j exp 2iH X j exp

2
f (cos(2H X ) + i sin (2H X ))

j
B j sin 2
exp
2
(1)
The summation is over all of the atoms j in the unit-cell with fj being the scattering power of the
jth atom at fractional coordinates xj,yj,zj represented in (1) by the vector Xj. The fj vary with both
the diffraction angle and the wavelength of radiation. The effects of local atom displacements on
the structure factors are expressed by the factor Bj, which in general is an anisotropic function
that is different for different atoms.
B
The structure-factor F(hkl) = F(H) is a complex quantity, and is related to the diffracted beam
intensity as I(hkl) = F(hkl).F*(hkl). The structure factor equation clearly allows us to calculate
117
F(hkl) and the corresponding intensity for any reflection once we know the atomic coordinates
of all of the atoms in the unit-cell. But in a normal diffraction experiment it is the intensity of
the reflection hkl that is measured, not its amplitude and phase. Therefore the phase information
is not obtained in an experiment, only the square of the amplitude. This is known as the phase
problem, and is the reason why crystallographers have jobs. In order to determine a structure,
one has to make a guess1 (intelligent or otherwise) at the positions of the atoms in the unit cell,
and then use this trial structure to calculate the F(hkl) and thus I(hkl) through Equation (1).
This first step is known as structure solution. In a high-pressure diffraction study this step is not
necessary unless the crystal has undergone a phase transition at high pressure, or has been
synthesized in-situ. The more common case is that one already knows the structure of the
crystal, and one is interested in determining the relatively small change in things like bond
lengths, angles or inter-molecular distances as pressure or temperature are changed. This
requires only the process of structure refinement. In this process the intensities calculated from a
trial structure (i.e. the structure at the previous pressure) via the structure-factor equation (1) are
compared to the observed intensities, and the parameters of the trial structure are then adjusted
so as to reduce the discrepancy between the calculated and observed intensity data.
The determination of the arrangement of atoms within a crystalline material therefore requires
the accurate measurement of the intensity of radiation diffracted by a sample of that material.
Both neutrons and X-rays can be used with both powder and single-crystal samples. The choice
between using X-rays or neutrons for high-pressure studies is essentially the same as for studies
at ambient pressure; neutrons are useful for samples containing both heavy and light atoms,
those in which it is necessary to distinguish between elements of similar atomic number, and
those experiments in which magnetic scattering is of interest.
For experiments conducted at high pressures inside environmental cells such as diamond-anvil
cells (DACs), the workflow of the experiment and data reduction is similar to that followed for
collecting an intensity dataset from a crystal in air. However, there are additional challenges to
be faced. The pressure cell restricts access to diffracted beams, limiting the resolution of the data
and making the final structure refinement more sensitive to individual data. At the same time,
the pressure cell typically reduces the signal level of the diffracted beams that can be measured
while increasing the background in the diffraction pattern. Lastly, the pressure cell will absorb
part of the X-ray intensity, and this absorption must be corrected if accurate and precise
structures are to be obtained by refinement. In this paper the principles for addressing these
challenges and obtaining high-quality data from high-pressure single-crystal X-ray diffraction
are summarized.
Diamond-anvil cells
Most high-pressure single-crystal X-ray diffraction measurements are performed in transmission

diamond-anvil cells, as illustrated in Figure 1. The essential features of this type of cell is that the
sample crystal is held in a pressure chamber filled with a hydrostatic fluid2. The chamber is
118
formed by a hole drilled in a gasket, often metal, and sealed top and bottom by the diamond
anvils. The incident X-ray beam is directed into the cell through one anvil, and the diffracted
beams pass out through the other anvil.
Figure 1. The essential geometry of a transmission diamond-anvil pressure cell for single-crystal diffraction.
The angles that these beams make to the load axis of the DAC are called the angles, I for the
incident beam, and D for the diffracted beam (Figure 1). The maximum angle of access for an
X-ray beam to the sample is denoted max. This is limited by the presence of non-absorbing
support plates for the diamond anvils. In order to obtain the maximum access to reciprocal
space of the sample, and thus obtain the maximum number of data, it is necessary to maximise
max when designing the DAC. The traditional solution3 was to support the anvils with backing
plates made of an X-ray transparent material, usually beryllium4, which were in turn supported
by an X-ray opaque material. This has the disadvantage that the backing plates absorb and thus
reduce the intensity of the X-ray beams and, in the case of polycrystalline beryllium, contribute
greatly to the background scattering in the diffraction pattern (Figure 2). The use of diamond
backing plates5 reduces the background but increases the absoprtion. More recently the BoehlerAlmax support has been developed6 which supports the anvils from the side, thus eliminating the
backing plates, and reducing both the absorption of the X-ray beams and the background
scattering from the cell (Figure 2, right).
119
Figure 2. Area detector diffraction images collected from (left) a DAC with beryllium backing plates and (right) a
Boehler-Almax DAC. Both frames show blank areas on the left-hand side due to shadowing by the DAC.
Data Collection
For most transmission DACs the body of the diamond cell restricts max angle to 40o or less. The
absolute maximum Bragg angle 2 of reflections that can be collected from a transmissiongeometry DAC is twice max , but at this angle only a very few reflections can actually be
collected. With max = 40o only one-third of the total number of reflections in the diffraction
pattern can be collected out to 2 = 60o. These restrictions apply equally whatever type of
detector, point or area detector, is being used. On an area detector the limits to the angles
appear on the data images as shadowed areas of the detector (Figure 2). For a point detector the
diffractometer control software is set up so that reflections obscured by the pressure cell are not
collected. Maximum access to reflections is achieved by operating the goniometer in fixed-phi
mode7, 8. Furthermore, the accessible reflections are not distributed equally over reciprocal space,
but are restricted to those reciprocal lattice vectors that are close to being perpendicular to the
axis of the DAC. In order to achieve high precision in all three fractional coordinates of all of the
atoms in the structure, one must therefore take care to ensure that the crystal is oriented in such
a way so as to allow access to as large a portion as possible of an asymmetric unit of reciprocal
space3 or to mounting two crystals of the same sample in different orientations together in the
DAC. The effect of the limited access can be predicted in advance by collecting a dataset in air,
restricting it9 according to the DAC limits10 and then perfoming a structure refinement on the
restricted dataset.
Background should be reduced as much as possible by collimating the incident beam so that it
does not strike the gasket, and it is recommended to use Boehler-Almax seats to reduce the
background, although some data integration software packages yield almost as good data quality
from Be-backed cells. In principle the background scattering is more divergent than the
diffracted beams from the sample, so one might expect that pulling the detector back would
120
improve the ratio of sample signal to background. In practise, the author has found this is not
the case.
Most diffraction intensity measurements from DACs are now performed with area detectors.
However, for crystals with small primitive unit-cells the traditional point detector instrument
typically yields better quality data in similar data collection times in a laboratory. This is because
the point detector can be collimated to remove background, it can collect only those reflections
that are accessible, it can be run in constant-precision mode to optimise the time spent
collecting each reflection, and full peak-profiling can be performed to recover weak intensities
and to identify and eliminate reflections affected by diamond diffraction events11.
Details on how to set up a data collection with an area detector depend in large part on the data
collection software. It is important to optimise the data collection parameters such as frame
width to the data integration method, in order to obtain the best data. In general, one should
optimise the data access by setting the DAC exactly face-on to the incident beam when the
diffractometer angles are zero, and collect the data in fixed-phi mode7, 8. The crystal must be
centered at the diffractometer center to within a few microns. The data collection should be set
up so as to collect only the accessible regions of reciprocal space and to obtain high redundancy
on symmetry-equivalent reflections. Commercial diffractometer control software should do this
automatically for the user. DACs typically absorb 60-70% of the X-ray intensity, so counting
times should be increased by a factor of 3 over the counting times used for the same crystal in
air.
Indexing and integration
In order to integrate area detector images to obtain intensities, the diffraction pattern of the
crystal must be indexed in order to allow the positions of the diffracted beams on the detector to
be predicted. Again, commercial software includes the necessary features; peak-hunting should
only be performed on the parts of the diffraction images that include the accessible regions of
reciprocal space. If not, the background evaluation will be wrong, and spurious peaks may be
found. This is simply achieved by specifying the opening angle max of the DAC to the peaksearch software. The peak search will normally find, in addition to the diffraction spots from the
sample, many other peaks. Some indexing software will succeed in indexing the sample
diffraction pattern even in the presence of many other peaks, other software may not. In the
latter case non-sample peaks need to be identified and deleted from the peak list. Peaks from the
diamond can easily be identified because they are much more intense than the sample peaks.
Harmonics of these peaks ( /2 and /3 are common) are more difficult to identify. Diffraction
spots from the pressure sensor will look like sample peaks and can only be identified by indexing.
Powder diffraction rings from Be backing plates, or from the gasket material, can be eliminated
on the basis of the d-spacings. With good software, the elimnation of the powder rings normally
leads to correct automatic indexing of either the sample, or a diamond or the pressure sensor
121
crystal. If the sample is not indexed the first time, delete the indexed peaks, and repeat the
indexing procedure on the shorter list.
Peak hunting will only find the stronger sample peaks from the sample. Once these reflections
have been indexed, the orientation of the crystal on the goniometer is obtained as an orientation
matrix or UB matrix. The unit-cell parameters are obtained directly from orientation matrix12.
Data integration to obtain the diffracted intensities from the sample proceeds by first calculating
positions on the detector of all possible diffracted beams from the sample crystal from this
matrix and the angular positions of the goniometer and the position of the detector when each
frame was collected. The background around each reflection must be evaluated, and subtracted
from the total intensity of the peak. The detailed methods applied depend on the software
package used. As for peak hunting, the software should mask and not use the area of the detector
obscured by the DAC body, otherwise false background levels will lead to incorrect integrated
intensities, even in the accessible regions of reciprocal space. Implementation of a number of
procedures inherited from point detector methods, including use of learnt profiles and local
background evaluation, certainly improves intensity data quality, as does the rejection of
diffraction peaks with abberant profiles, which is a strong indication of reflections affected in
some way by diamond diffraction11, 13.
In principle, the value of the max angle should be known from the design of the DAC. However,
if the crystal is even slightly off-center in the DAC, the effective opening angle is frequently a few
degrees less than expected. One easy test to perform is to restrict integration (or edit the
integrated data) to different values of max and compare the Rint obtained from averaging the
intensity data. As shown in Figure 3, the value of Rint will increase as soon as data with > max
is included, because obscured reflections of low or zero intensity will be included in the
averaging. Because reflections with higher Bragg angles occur, on average, with higher values of
, the increase in Rint is most obvious in the high-angle reflections (Figure 3).
Figure 3. The variation with max set in the integration of Rint on one data set collected from a crystal in a DAC with
Boehler-Almax seats. The plot indicates that the effective max = 36o.
122
Absorption
When X-rays pass through any material they are partly absorbed. The intensity of the
transmitted beam depends on the original intensity I0, the path length t of the X-rays in the
material and the absorbing coefficient of the material as
I = I 0 exp(t ) . Values of for any
material can be calculated from the values tabulated in International Tables for
Crystallography14. The transmission coefficient T = exp( t ) and the measured diffracted

beam intensities Iobs are used to obtain the intensities I corr = I obs .T
corrected for absorption.
In a diffracting crystal the path lengths of the incident and diffracted beams vary across the
crystal and the expression for the transmission coefficient for a reflection intensity becomes an
integral over the crystal volume, V, of the path lengths of the incident (tI) and diffracted beams
(tD):
T = V 1 exp( (t I + t D ))dV
(2)
For a crystal mounted in a pressure cell, corrections also have to be made for the absorption by
the components of the pressure cell through which the X-rays pass. The general expression for
the transmission coefficient becomes15:
T = V 1 exp
The factor exp
(t
i
Ii
(t
i
Ii
+ t Di )dV
(3)
+ t Di ) is the total transmission factor associated with a volume
element dV of the crystal that is illuminated by the incident beam, being a sum over the path
lengths of the beams in all of the components of the DAC. For experiments in which the beam is
smaller than the crystal, the integration is over the illuminated volume and an additional
normalization for the illuminated volume of the crystal must also be applied.
There are two general approaches to correcting measured intensities for the effects of
absorption. The empirical approach13, 16, often called frame scaling, is to apply scale factors to
the intensities that are functions of the incident and diffracted beam angles, or the goniometer
angles. These scale factors can be expressed in several ways; often spherical harmonics or
polynomials are used. The scale factor parameters are adjusted until the agreement between the
symmetry-equivalent intensities is maximised, and thus Rint is minimised. The big advantage of
this approach is that it is completely empirical, requiring no user input. The disadvantage is that
the corrections have no physical basis and, for a DAC experiment they may therefore be
unreliable because of the low number of equivalent reflections, the fact that equivalent
reflections tend to have similar transmission paths through the DAC, and the larger number of
outliers in the data. Thus, for DAC data analytical absorption corrections based on application of
equation (3) and a physical description of the experiment are recommended. The detailed
123
methodology and its historical development have been described previously17, and a modern
version of the ABSORB program18 which greatly reduces the difficulties of setting up the
calculations, will be presented in a workshop at this meeting. Modern practise is to first apply an
analytical absorption correction as precisely as possible, followed by an emipirical correction
that then corrects for both any small inaccuracies in the analytical correction arising from
uncertainties in the measurement of the DAC and crystal and corrects for beam illumination
variations. The latter is especially important for laboratory measurements made with microsource X-ray tubes when the width of the beam is similar to the diameter of the sample crystal.
This dual approach is implemented in commercial software packages.
Averaging
As indicated in Figure 1, the diffraction from the diamond anvils can interfere with the measured
reflection intensities. When the beams diffracted from the diamonds fall near to sample
reflections, they modify the background or peak shape or the peak intensity of the sample
reflection. Such reflections are often identified and eliminated during integration. In addition,
the diamond anvil on the incident-beam side of the cell may diffract away some of the incident
intensity. Or the anvil on the detector-side of the cell may diffract away part of the diffracted
beam from the crystal. In both cases the measured reflection intensity is reduced19, but the peak
shape remains the same so affected reflections cannot be easily identified during data
integration. However, they may easily be detected after data collection by comparing the
intensities of symmetry-equivalent reflections and rejecting those reflections (so-called
outliers) whose intensities differ significantly from the average of the set of equivalents. Such a
procedure with a sound statistical basis has been available for many years20 and can be modified
for DAC data by making use of the fact that the reflections affected are always reduced in
intensity. These are then rejected in a first-pass through the dataset by applying the Blessing
criteria to only those reflections with intensities less than the mean intensity of the set of
symmetry-equivalent reflections21. A second pass through the unrejected data is then performed
to average the remaining data according to the normal statistical criteria20. This combined
procedure also serves to remove individual outliers that may arise from a variety of other causes.
Refinement
In principle, structure refinement to diffraction data collected at high pressures should proceed
exactly as a refinement to data collected at room conditions. In reality, however, the limited
resolution and lower signal to noise will degrade the quality of the data and thus the refinement.
Furthermore, however well the corrections to intensity data are made, they are never perfect.
Taken together these effects mean that there are often systematic errors in the structural
parameters determined for crystals held in diamond cells. These systematic errors can be
identified by making measurements of the crystal at room conditions in the DAC, and
comparing the results to those obtained from measurements made from the same crystal in air.
This provides a test of both the data reduction methods and an indication of the problems
124
created by limited data resolution. The reliability of structure refinements can be improved
further by the application of two well-known statistical methods in the refinement. The process
of robust-resistant refinement22 allows residual outliers that remain in the dataset to be
automatically identified and down-weighted, and the normal probability plot23, 24 can be used
as a guide to the reliability of the weighting scheme. Alternatively, some refinement packages
such as Jana25 provide tools for the graphical identification of outliers. In the future, with the
availability of increased computing power, one expects the methods of parametric refinements
already implemented for high-pressure powder diffraction26 to also be used for single-crystal
studies.
Conclusions
With reasonable care in setting up the experiment, and by using intelligently the software tools
now available, one can obtain refined crystal structures at high pressures that approach the
quality of crystal structures refined to data collected at ambient pressure. The major limitation in
refinement resolution is the result of the limitations to access in reciprocal space imposed by the
body of the DAC. This can in part by alleviated by collecting data at shorter wavelengths than
the conventional Mo radiation used in many laboratories. And it can be overcome by collecting
data from multiple single crystals mounted in different orientations within the DAC.
Acknowledgments
References
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126
An introduction to X-ray Absorption Spectroscopy
An introduction
to X-ray Absorption Spectroscopy
Sakura
Pascarelli, ESRF
email: sakura@esrf.fr
Sakura Pascarelli
European Synchrotron Radiation Facility, Grenoble, France

sakura@esrf.fr
Abstract
This lecture will give a general introduction to X-ray Absorption Spectroscopy. It aims a large
audience, with diverse academic background. A brief summary of the fundamental X-ray-matter
interactions and X-ray based techniques will be followed by a description of the photoelectric
effect. The linear absorption coefficient and its measurement will be introduced. I will then
describe in a qualitative way the origin of XAFS, the fine structure that appears above an
absorption edge in condensed matter.
Keywords
X-ray Absorption Spectroscopy, EXAFS, XANES, photoelectric absorption

Fundamental interactions and main X-ray techniques
The use of X-rays to investigate the properties of matter at the atomic scale is based on two
fundamental X-ray matter interactions:
1.
Photoelectric absorption. Here an X-ray photon disappears after having excited a
core electron belonging to an atom in the sample. This process leaves the absorber atom in
an excited state, because now there is a hole in the core level. For photoelectric absorption
to occur, the energy of the X-ray photon needs to be larger than the binding energy of the
core electron. The core electron can be excited to a bound state (the electron occupies a
higher available - level of the same atom, with lower binding energy), or to the continuum
(i.e. the electron travels like a free particle, and no longer feels the attractive potential of the
absorber atom). In the latter case, we call it a photoelectron. Its kinetic energy is equal to
the energy of the incident X-ray photon minus the binding energy of the initial core level. As
you will see in what follows, the photoelectron is a very important particle in X-ray
absorption fine structure spectroscopy.
2.
Elastic or inelastic scattering. Here, an incoming X-ray photon interacts with the
electronic potentials of the atoms in the sample, or with phonons, or any other collective
excitation, and then leaves the sample. This is a photon in/photon out process. The photon
can preserve its energy (elastic scattering) or loose part of it (inelastic scattering).
a) Elastic (Thompson) scattering: Imagine the photon (particle) as an electromagnetic
(EM) wave that oscillates with a given angular frequency (proportional to its
energy), and lambda its wavelength (inversely proportional to its energy). The
127
electric field of this wave accelerates the electrons, which start oscillating at the
same frequency. These oscillating electrons then emit EM waves (due to
Maxwells equations) of the same frequency. This process occurs when the energy
of the photon is small compared to the mass energy of the electron.
b) There are different kinds of inelastic scattering:
- Compton Scattering: The energy of the incident X-ray photon is much larger than the
binding energy of the atomic electron, so all electrons can be treated as being free.
When the energy of the photon becomes comparable to or larger than the mass of the
electron, then the photon transfers some of its energy to the electron. In this process,
the photon, seen as a particle, hits the electron, and transfers some of its energy and
momentum to it. In Compton scattering, the frequency of the scattered photons is
lower than that of the incident radiation.
- Resonant Inelastic X-ray Scattering (RIXS): The incoming X-ray (of energy and
momentum k), excites an electron from a deep-lying core level into the empty valence.
The empty core state is subsequently filled by an electron from the occupied states
under the emission of an x-ray (of energy and momentum k). This RIXS process
creates a valence excitation with momentum k k and energy .
- Non-resonant Inelastic X-ray Scattering (X-ray Raman Scattering or XRS): a highenergy X-ray photon (of energy and momentum k), gives energy to a core electron,
exciting it to an unoccupied state. The emitted photon has energy and momentum
k . The process is in principle analogous to photoelectric absorption, but the energy
transfer E= - plays the role of the X-ray photon energy absorbed in x-ray
absorption.
Based on these fundamental photon-matter interactions, we can also roughly distinguish two
families of experimental techniques:
1.
2.
128
Spectroscopy: probes properties of matter through the excitations that are induced by
the loss of energy of the photon in its interaction with matter. We can learn about the
electronic structure (core-electron excitations, valence properties, ) or about the local
structure around an absorber due to the photoelectron scattering from neighbor atoms.
Techniques are: XAS, EXAFS, XANES, Inelastic X-ray Scattering, Resonant Inelastic Xray Scattering, X-ray Emission Spectroscopy, X-ray Raman Scattering, etc...
Elastic diffusion: probes the geometric structure at the atomic level through the elastic
scattering of X-rays (no loss of energy). For crystalline solids, we refer to the term
diffraction (X-ray Diffraction, Grazing Incidence XRD, ), whereas we use the term
scattering for disordered matter - amorphous solids, liquids, etc (X-ray Scattering,
Wide Angle X-ray Scattering, Small Angle X-ray Scattering..)
The linear absorption coefficient

X-ray absorption spectroscopy deals with the measurement of the linear absorption coefficient,
. It is defined as follows:
I = I0 e
Figure 1.
where
I 0 and I
are respectively the incident and transmitted X-ray flux (number of photons
per second), and t is the thickness of the sample. This expression can be easily obtained by
calculating the decrease of intensity
dI
as the photons travel through the sample of atomic
surface density N (atoms/cm ) and thickness t (cm) :

2
dI =
I (x ) N
dx
a
t
dI
t
=
N a dx
0 I (x )
t 0
ln I (t ) ln I (0) =
N a
t
I (t )
=
e N =
e t
I (0)
a
a()is the atomic cross section, expressed in cm2/atom. The absorption coefficient is a function
of photon energy , or of the angular frequency and its dimensions are [length -1]:
( ) = a ( )
N
N
= a ( ) a
t
A
cm
at
2
at
mole
g
mole
g
cm3 =
[cm ]
1
Na , A and are Avogadros number (atoms/mole), the atomic weight (g/mole) and density
(g/cm3) respectively. In general, you can find tabulated the mass absorption coefficient /:
= a
Na
A
at
cm mole
at g
mole
2
cm 2
g
129
In principle all processes that contribute to attenuating the X-ray flux upon transmission
through the sample are included in the linear absorption coefficient, : photoelectric absorption
(the photon disappears), elastic or inelastic scattering (the photon is deviated, so it is no longer
present behind the sample) are all processes responsible for the attenuation of the X-ray flux
through the sample.
The measurement of the absorption coefficient
In XAS, we are interested in the measurement of as a function of X-ray photon energy. We
therefore need an intense source of X-rays in a large and continuous energy range. Bending
magnets at high energy synchrotrons are excellent sources for XAS. The bending magnets at the
ESRF (a 6 GeV storage ring) produce a continuous spectrum of X-rays with critical energy
around 20 keV. These sources can be optimally used for XAS applications from a few keV to ~
100 keV.
Double crystal monochromators are used to produce a monochromatic beam with a fixed exit.
The energy of the X-rays is selected by Bragg diffraction on the first crystal. The second crystal
(parallel to the first) restores the initial propagation direction. By rotating the Bragg angle, the
energy of the diffracted beam can be tuned while maintaining a fixed exit position and direction.
The sample is positioned between two ion chambers (or other X-ray detectors), that measure
I 0 and I . When we measure an absorption

spectrum in transmission geometry, we measure I 0 and I at each energy (or Bragg angle) step,
respectively the incoming and transmitted flux
and we calculate:
ln
I0
I
Figure 2.
The absorption coefficient is a function of energy
The absorption coefficient is a rapidly decreasing function of energy (~ E -3):
130
Z4
A E3
It also depends strongly on the atomic number Z, on the density and on the atomic mass A.
The absorption coefficient as a function of energy also has sudden jumps (absorption edges)
which occur at energies that are characteristic of the element.
Figure 3.
For example, in the energy range 1-100 keV Oxygen has no absorption edges, Iron has one at
around 7 keV, and Cd has a few around 2-3 keV and one around 30 keV and Pb has edges at ~ 4
keV, 10-20 keV and at ~ 90 keV.
Contributions to the absorption coefficient
Lets have a closer look at the linear absorption coefficient of one element, for example Ge. In the
figure below we plot all the contributions to the total absorption coefficient: photoelectric
absorption, elastic and inelastic scattering. We see that photoelectric absorption dominates the
absorption coefficient in this energy range
Figure 4.
For this reason, we will concentrate only on photoelectric absorption.
131
Photoelectric Absorption
X-rays are absorbed by all matter through the photoelectric effect, depicted in the figure below.
An X-ray is absorbed by an atom when the energy of the X-ray is transferred to a core-level
electron (K, L, or M shell) which is ejected from the atom. The atom is left in an excited state
with an empty electronic level (a core hole). Any excess energy from the X-ray is given to the
ejected photoelectron. The kinetic energy of the photoelectron Ekin is given by:
p2
Ekin =E E0 =
2m
where E is the incident X-ray photon energy, E0 is the binding energy of the core-level electron,
p and m are the photoelectron momentum and mass.
Figure 5.
Radiative and Non-Radiative De-excitation

When X-rays are absorbed by the photoelectric effect, the atom in an excited state (presence of
the core-hole) will relax back to the ground state. A higher level core electron fills the core
hole, and a fluorescent X-ray or Auger electron is emitted. The former process is referred to as
radiative de-excitation more probable for heavy elements, while the latter is referred to nonradiative de-excitation more probable for light elements. X-ray fluorescence and Auger
emissions occur at discrete energies characteristic of the absorbing atom, and can be used to
identify the absorbing atom.
Radiative De-excitation
Non-radiative De-excitation
Figure 6.
132
XAS measurements
XAS measures the energy dependence of the X-ray absorption coefficient (E) at and above the
absorption edge of a selected element. Generally (E) is measured in two ways:
Figure 7.
Transmission: The absorption is measured directly by measuring the photon intensity

transmitted through the sample:
I = I0 e
( E )t
(E ) t = ln 0
I
Fluorescence: The re-filling of the deep core hole is detected. Typically the fluorescent X-ray is
measured:
(E )
IF
I0
It is important to underline that the only exact measurement of the absorption coefficient is in
transmission. However, this is not always technically possible. For example, if the sample is
deposited on a thick substrate ( no photons behind the sample), or if it is very dilute in a highly
absorbing matrix ( very little contrast at the edge).
Recipe for calculating sample thickness for transmission XAS
Here is a recipe for calculating the ideal thickness t of a sample for a measurement of XAS in
transmission:
1. Calculate the total absorption coefficient for your sample. For a generic sample PxQy.:
=
tot
A
x P
P M
A
y Q
Q M
where Ai/ M is the mass fraction of element i .
2. Choose t so that the total absorption t of the sample at an energy just above the absorption
edge of interest is maximum 2 or 3:
133
above edget < 2 3

3. Check that with this t, the contrast at the absorption edge (also called the jump J) is high
enough (ideally it should be close to 1):
Jump = [ above edge below edge ] t 1
If the absorber element is very dilute, and the matrix absorbs a lot, then the Jump will be too low
(J <0.1). In this case, detection of fluorescence could provide a better measurement of the
absorption coefficient.
What is XAFS?
X-ray Absorption Fine Structure is the oscillatory variation of the X-ray absorption as a function
of photon energy beyond an absorption edge.
2.40
2.20
Absorption
2.00
1.80
1.60
1.40
1.20
1.00
0.80
12000
12400
12800
E (eV)
13200
Figure 8.
We shall see that these oscillations appear because the proximity of neighboring atoms strongly
modulates the absorption coefficient. The As K-edge absorption spectrum of a pseudo-binary
semiconductor InAsxP 1-x is plotted in the figure above.
EXAFS and XANES
XAFS is also referred to as X-ray Absorption Spectroscopy (XAS) and is broken into 2 regimes
(see also figure below):
XANES:
EXAFS:
X-ray Absorption Near-Edge Spectroscopy
Extended X-ray Absorption Fine-Structure
which contain related, but slightly different information about an elements local coordination
and chemical state. The XANES extends up to a few 10s of eVs above the edge (blue area). The
EXAFS may extend up to 1000eV or more above the edge (pink area).
134
Figure 9.
In the XANES region, transitions are to unfilled bound states, nearly bound states, or to the
continuum, where the photoelectron has a low kinetic energy (Ekin ~ few eVs). In the EXAFS
region, the photoelectron is always excited into the continuum, and has a kinetic energy that is
much larger (Ekin ~ 50-1000 eV). High energy electrons do not travel much in matter, i.e. their
mean free path is limited to a few , as shown in the plot below. It is the difference between the
kinetic energy of the photoelectron that essentially differentiates these two regimes. Thanks to
the very low mean free path of the photoelectron, approximations can be used to interpret
EXAFS, that are not valid for XANES. For this reason, the fine structure that appears in the
XANES and EXAFS region cannot be analized in the same way.
Figure 10.
EXAFS qualitatively
EXAFS is a quantum phenomenon, and it cannot be understood without invoking the dual
nature of elementary particles. We know that, depending on the experiment, particles can
behave as waves, and waves can behave as particles.
135
In quantum mechanics, electrons are described by a wavefunction, (r,t), a function of space

and time. (r,t) is the probability amplitude of finding the electron at position r at time t, so that
its square modulus (r,t) is a positive real number :
(r , t ) = (r , t ) * (r , t ) = (r , t )
2
and represents the probability density that the particle is at position r. If the particle is measured,
then there is 100% probability that it is somewhere:

+
dr (r , t ) (r , t ) = 1
*
Qualitatively we can explain EXAFS with the following picture:

1. The absorption coefficient is proportional to the probability that the X-ray photon is absorbed
by photoelectric effect. This in turn is proportional to the probability of finding the electron
(core electron, then photoelectron) at a specific point in space and time (no electron no
photon absorption).
2. The energy dependence of the absorption coefficient will have wiggles (EXAFS) if the
absorption probability changes with energy, i.e. if the probability of finding the electron at a
specific point changes with energy .
3. Lets consider an X-ray photon of energy E and an atom with a core-electron of binding energy
E0. The spatial extent of the core-electron wavefunction is very small on the scale of the atom, as
it is very close to the nucleus. So the core-electron wavefunction (r) can be approximated
with a delta function at the origin: (r) ~ (r).
4. If the incident photon has sufficient energy (E > E0), then the photon will be absorbed by
photoelectric effect, and a photoelectron will be created, with kinetic energy:
Ekin =E E0 =
p2
2m
This electron can be also visualized as a spherical wave that propagates away from the absorber
atom, with wavevector k and wavelength :
Ekin =E E0 =
2 k 2
2m
2
k
5. If the atom is isolated (no neighboring atoms): The photoelectron, represented by the
outgoing blue solid circles in the figure above, will propagate freely away from the absorber atom
(left panel figure 11). The absorption coefficient (probability of finding the electron at the origin)
is a smoothly decreasing function of E. To understand this, lets consider two extreme cases:
136
Figure 11.
a. E=E0 : the photoelectron has zero kinetic energy. All its wavefunction is concentrated
at the origin because it cannot travel far (dark blue rectangle in the figure 11 below). The
probability of absorption is maximal.
b. E>>E0 : the photoelectron has a very large kinetic energy. It can travel far from the
origin, its wavefunction is distributed over a very large spatial range (light blue rectangle in
figure 12 below), but the integral over all space is still equal to 1, so there is less probability of
finding it in the origin. The probability of absorption has decreased.
Figure 12.
6. If the atom is not isolated (presence of neighboring atoms): In figure 11 (right panel), R
indicates one of the interatomic distances, is the wavelength of the photoelectron wave. The
outgoing photoelectron wave interacts with the electron potentials of the neighboring atoms,
and portions of this wave are backscattered (red dotted circles) towards the origin. This is an
elastic process, so the energy of the photoelectron (its wave-vector and its wavelength) does not
change (the solid and the dotted waves have same ).
The auto-interference of the photoelectron wave - the interference pattern created by the
outgoing (blue solid line) and the incoming (red dotted) circles - modifies the absorption
coefficient value. To understand why the absorption coefficient wiggles as a function of photon
energy, lets consider what happens to this pattern when E changes:
a. As E is scanned above E0, Ekin is varied, and consequently k and . So the ratio /R
varies as a function of E.
137
b. The outgoing and backscattered parts of the wave interfere either constructively or
destructively, depending on the ratio /R (see figure below).
c. The interference between outgoing and incoming waves gives rise to the sinusoidal
variation of (E), i.e. the probability of finding the electron in the origin (amount of
wave-function at the origin) oscillates from high (constructive interference) to low
(destructive interference) as a function of photon energy E.
Figure 13.
The frequency of the oscillations is proportional to the distance R. The amplitude is proportional
to the number of neighbors, their spatial distribution and their type.
XAFS : Main applications
Diffraction methods (using X-rays, neutrons, electrons) applied to crystalline materials with
long-range order provide a 3D picture of atomic coordinates. When applied to materials with
only short-range order (amorphous solid, liquid, or solution), they provide a 1D radial
distribution function containing interatomic distances due to all atomic pairs in the sample.
XAFS always provides a 1D radial distribution function centered at the absorber. It therefore
has element selectivity (one can choose the absorber atom). It provides structural information on
the environment of each type of atom: distance, number, kind, static and thermal disorder. It is
sensitive to 3-body (and generally n-body) correlations through multiple scattering paths.
EXAFS is very short-sighted, it has high accuracy within a few from the origin. It has higher
sensitivity to local distortions (i.e. within the unit cell), but is not sensitive to structure beyond a
few coordination shells. It allows the investigation of matter in the solid (crystalline or
amorphous), liquid, solution or gaseous state with same degree of accuracy. Through the
XANES features, it is sensitive to charge state, and to the density of empty states above the Fermi
level.
138
Typical applications are those that exploit its element selectivity and its local structure
sensitivity:
Local structure in non-crystalline matter
Local environment of an atomic impurity in a matrix of different atomic species
Study of systems whose local properties differ from the average properties
Detection of very small distortions of local structure

References
1. Introduction to XAFS: A Practical Guide to X-ray Absorption Fine Structure Spectroscopy, G. Bunker,
Cambridge University Press, 2012
2. X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS, and XANES, in Chemical
Analysis, D. C. Koningsberger and R. Prins, ed., John Wiley & Sons, 1988
3. International XAFS Society: http://ixs.iit.edu/
4. Tutorials and other Training Material: http://xafs.org/Tutorials
139
Ices, salty ices and ice clathrates structures.

Livia E. Bove
Ices, salty ices and ice clathrates structures

Livia E. Bove
CNRS-UMR 7590 P&M Curie Univ., Paris, France

livia.bove@epfl.ch
Introduction
Despite its rather simple electronic and molecular structure, water manifests a range of
anomalies, with respect to other simple molecules, that account for its crucial role in nature.
Waters uniqueness derives from the conjunction of the molecules open geometry (Figure 1),
and the presence of weak intermolecular hydrogen bonds (HB) (Figure 2). The geometry of a
water molecule is dictated by the hybridisation of the molecular orbitals, which produces an
almost tetrahedral H-O-H angle. This represents a key point for understanding water properties
and ice richness of polymorphs (Figure 3) [Finney04, Petrenko]. Puckered hexagonal and nearplanar ring structures, as well as pentagonal rings can be observed in most ice phases. These
peculiar structures are determined by the HOH angle (104.474 in the gaseous molecule)
[Benedict56], which is close both to the tetrahedral angle (ca. 109.5 ) and to the internal angle of
a pentagon (108 ). Other tetrahedral coordinated systems, such as SiO2 and Si, also form a wide
range of crystal structures, however, water builds them through hydrogen bonding, with an
equal number of hydrogen- bond donors and acceptors, and this is somehow unique.
Figure 1. Average geometry and charge distribution of the water molecule. The experimental values for gaseous water
molecule are O-H length 0.95718 , H-O-H angle 104.474. Diffraction studies in liquid water (O-H length 1.01 , O-D
length 0.98 [Soper08]; O-H length 0.990 , O-D length 0.985 [Salmon12].
Figure 2. Schematic view of the inter-molecular bonds between water molecules. R is the O---O distance, is the donor
angle and is the acceptor angle. The potential directed along the broken line between the two oxygen atoms is strongly
anisotropic.
140
Hydrogen bonding, i.e. the electrostatic attraction between hydrogen atoms and the negatively
charged region in the back of the Oxygen site (Figure 2) [Savage86, Hermansonn84], accounts
for most of thermal anomalies of water, not last of them is that water is a liquid at the conditions
we find on the Earths surface. Actually, if compared to the hydrides of other elements close to
oxygen in the periodic table, namely methane, ammonia, hydrogen sulphide, and so on, water is
the only one which is not gaseous at room temperature.The energy of the hydrogen bond (HB)
lies in between simple van der Waals forces and ionic ones: it is of the order of 15 times a
thermal fluctuation at ambient temperature (5 kcal mol-1, i.e. around 1000 K), that is
substantially above the domain of existence of the liquid phase at atmospheric pressure.
Quantum mechanical calculations [Hermansonn84] show that the overall charge distribution of
a water molecule is rather diffuse, and nearly trigonal. Thus the classical symmetric picture of
tetrahedrally-disposed positive charges at the hydrogen site (D+) and two distinguished lobes of
negative charge (D-) in correspondence of oxygen site, is thus actually over simplistic.
Figure 3. The phase diagram of ice. Note that ices IV and XII are metastable phases that can be found within the stability
region of ice V. Adapted from [Finney_review]
Nevertheless the classical tetrahedral arrangement of the first-neighbour environment of a water

molecule, with hydrogen-bonds with four neighbours, two of which are HB donors and two HB
acceptors, remains the preferred mutual arrangement of H-bonded water molecules and
represents the central motif of water in practically all its condensed phases.
Crystalline ice phases
Looking at the multiplicity of ice structures generated under different p-T conditions (Figure 3),
we can remark that all ice phases are formed by molecules connected according with this fourcoordinated motif. As an example, the open and low-density structure of ordinary ice is formed
by hexagonal rings of four-folded water molecules (Figure 4). The low density is actually a
consequence of the angular constrains dictated by the directionality of water-water interaction
(Figure 2). The HB bonded O-O distances and the O-O-O angles vary only very slightly in this
structure.
141
When subjected to moderate pressure, i.e. few hundreds of MPa, it transforms to denser phases
such as ice II or ice III, which, though still quite open, show the appearance of five or four
membered rings.
Figure 4. Open arrangement of water molecules in ice Ih (left) and ice II (center) as seen looking down the c
crystallographic axis. Note in ice II the appearance of pentagonal and tetragonal rings. The structure of ice IV (right)
shows two interpenetrating tetrahedral motifs; reproduced from [Finney_review].
In these phases the spread of both bond lengths and bond angles is increased. In particular
deviations up to 30 of the tetrahedral angle are accepted, pointing at the relative softness of the
orientational part of the water-water potential. As pressure is further increased, the structure
accommodates more molecules in a reduced volume by threading hydrogen bonds through some
of the open HB hexagonal rings, always retaining the tetrahedral motif (Figure 4).
All high-pressure ice phases, such as ice VI, VII and VIII are built by two interpenetrating sublattices of four-coordinated motives. As a result of this interpenetration of low-pressure
structures the system experiences a large densification and the degrees of freedom for
rearrangement under further compression reduce. Above about 2 GPa, only two molecular
phases are known, ice VII and VIII (Figure 5). Ice VII is composed of two interpenetrating but
not interconnected tetrahedral hydrogen-bonded networks of water molecules of normal cubic
ice, Ic, with a body-centered-cubic (b.c.c.) oxygen structure. The orientation of the water
molecules is disordered, resulting in a paraelectric phase. In the antiferroelectric ice VIII phase,
the water molecules and the associated dipole moments on the two sublattices posses long-range
order and the dipoles point in opposite directions promoting a slight tetragonal distortion of the
cubic unit cell along the direction of staggered polarization. In these two phases the hydrogen
bonds are characterized by a pronounced double-well proton transfer potential. Upon further
reducing the distance between donor and acceptor oxygens the proton potential degenerates
into a single-well potential [Marx99], giving rise to a symmetric or centered hydrogen bond,
where hydrogen atoms are located midway between two neighboring oxygen atoms. Infrared
(IR), Raman and more recently X-ray measurements [Gonchy99] have provided evidence for the
transition in water from the molecular phases ice VII and ice VIII to an atomic phase with
symmetric hydrogen bonds when the distance between acceptor and donor oxygen atoms
decreases below 2.3 (at about 60 GPa). Quantum effects play an essential role in the
phenomenon of hydrogen bond centering, thus the description of ice VII and ice VIII
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transformation to the atomic ice X represents a stringent benchmark for theoretical calculations
[Marx99, Car11, Millitzer13, Bronstein14].
Figure 5. Structure of proton disordered ice VII (left), proton ordered ice VIII (middle), and proton centred ice X phase
(right). The O lattice is constituted of two interpenetrating ice Ic lattices.
Salty ice at GPa pressures: the maxing of salty ice VII
Frozen water is normally unable to incorporate large amounts of salt (Figure 6). This property is
important for our climate, because, when seawater freezes, a solution of higher salinity, so-called
brine, is expelled. Since this has a higher density than seawater, it sinks and drives oceanic
circulations in the polar region. The inability of ice to incorporate ions is not exclusive to the
ordinary ice Ih phase, but applies to all the low-pressure phases, including the low-density
amorphous phase of ice. Based on this observation made at ambient pressure, the presence of
salts dissolved in water was always disregarded when dealing with its solid phase. However, most
of the water on Earth exists in form of salt water, and it becomes more and more evident from
space mission data [McCord01,Lorenz08] that this is also the case for the icy satellites of the
giant planets. As examples: chemical analysis of the geysers emanating from the south pole of
Enceladus by the Cassini space probe indicate a water salinity close to what is found on Earth
[Postberg11], while the Europa and Ganimede weak magnetic moment confirms the likelihood
of a salt water ocean under the surface.
Up to our recent studies [BoveNatMat09, BovePRL11, LudlPCCP15, Ludl_unpubl,
BovePNAS15], the high-pressure phase diagram of salty ice was almost unexplored [Frick06]. A
few monohydrates and di-hydrates of simple salts were known to exist in nature and be stable
under pressure, such as LiClH2O, LiBrH2O, LiIH2O, NaCl2H2O, NaBr2H2O, NaI2H2O, LiI2H2O
and LiI3H2O. However, these are structurally unrelated to any form of pure ice.
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Figure 6. (left) Observation of salt-hydrates formation when cooling a salty NaCl water solution (A. Ludl); (right)
snapshot of simulations by [Vrbka06] showing solute expulsion from the forming ice Ih lattice while cooling an aqueous
solution.
The situation can indeed be strikingly different if ice phases are produced by recrystallization of
amorphous salt solutions under high pressure. This route produces high-pressure ice phases
capable to incorporate in their structure substantial amounts of salt, and showing unusual
structural and physical properties. Our studies suggest that there could be a whole new class of
salty high-pressure ice forms whose characterisation could be relevant for the description of ice
bodies in the Universe. The discovery of the existence of salty ices under pressure was
unexpected. Contrarily to pure water, where compression of HDA or VHDA phases above 2 GPa
results in recrystallization of ice VIII [Klotz03], the dense amorphous salty ice phase (saltyVHDA in the following) described in [BovePRL2013] can be compressed up to pressures above
10 GPa without undergoing crystallization. Upon compression, salty-VHDA shows a strong
pressure-induced shift as well as a substantial narrowing of the main peak at Q = 2.12.5 1.
Already at 3.3 GPa, for example,the main peak position is considerably higher than for any highdensity or very high-density amorphous ice under pressure, which indicates the high capability
of salty amorphous ice to densify. When this salty-VHDA form is warmed up at 4 GPa, the peak
width continues to reduce, and this effect carries on up to almost room temperature. However,
at 271 1 K, a sudden crystallization occurs, accompanied by a small but detectable drop in
pressure, as shown in the inset of Figure 7. Neutron diffraction unambiguously enables to assign
this new crystalline structure to ice VII, i.e. the phase of pure ice that is expected to occur at this
temperature and pressure (see inset Figure 7). Ice VII crystallizes in space group Pn3m with O at
(1/4,1/4,1/4) and H at (0.41, 0.41, 0.41) with site occupancy 0.5. This produces an average
structure with oxygen on a body-centred-cubic (b.c.c.) lattice, and twice as many H sites as
hydrogen atoms available. The diffraction pattern further shows the so-called Huang diffuse
scattering, characterized by tails under the main reflection peaks (Figure 8). Such a phenomenon
is produced by the scattering from the strain field of interstitials and, together with the evidence
given further below, is a fingerprint for incorporation of Li and Cl into the ice VII structure.
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Figure 7. Sequence of patterns during crystallization at 4 GPa and 265276 K. The reflections marked by asterisks are
due to the lead pressure marker. The inset shows the pressure variation during crystallization, derived from the refined
lattice parameters of Pb. The patterns in the main figure correspond to data points at 264, 270, 273 and 276 K (see
insert).
The Rietveld fit of the diffraction data (Figure 8) revealed two main effects: firstly, the refined
unit cell volume is 8% larger than expected for pure ice VII at this pressure and temperature;
secondly, unusually large displacement factors are found both for oxygen (x21/2 = 0.34 ) and
deuterium (x21/2 =0.35 ), an effect that cannot be attributed to thermal motion but must arise
from large positional disorder.
Figure 8. Diffraction pattern of LiCl6D2O at 4 GPa and 280 K. The line through the data (circles) is a Rietveld fit to the
pattern based on the ice VII structure, and the difference plot is given below. Tick marks indicate positions of reflections,
red stars the fitted reflections. The anomalously strong-Debye Waller factor is evident from their drop in intensity with
Q. The red arrow indicates the diffuse Huang [Huang10] scattering and the drawing on the left depicts the mechanism
generating this diffuse intensity. The inset shows schematically the pressuretemperature path before crystallization
superimposed to the phase diagram of pure water.
145
Finally, upon cooling below 270 K, pure ice VII transforms into its hydrogen-ordered form, ice
VIII. As mentioned early (see Introduction), this consists of two interpenetrating networks with
H2O dipoles pointing in well defined opposite directions along 001. Conversely, the salty-ice
shows a pattern strictly identical to the one collected at high temperatures down to 80 K. The
observation of Huang scattering, the unusually strong attenuation of Bragg reflections, the
expanded lattice parameters, and the non-recovery of the ordered phase VIII under cooling,
conclusively suggest that the Li- and Cl+ ions are incorporated into the ice VII structure, rather
than being expelled into grain boundaries.
The number of possible sites for Li- and Cl+ in the structure of ice VII is actually very limited.
Published structural data for the salt hydrates, LiClH2O, LiBrH2O show that Li+ always adopts
an octahedral coordination. This is true also in its glassy VHDA phase, which acts here as
precursor of the salty ice VII crystal (Figure 9). Li+ adopts a 6-fold coordination in the saltyVHDA phase [BovePRL2013], which thus favours the inclusion of the ion, upon crystallization,
in the interstitial position located at the face centre of the ice VII unit cell. Due to the similarity
in molar volume between the Cl- ion and a water molecule, the most likely positions of the anion
within our proposed structure are the oxygen substitutional lattice sites preferentially in the
vicinity of a Li+ cation. Incorporation of Li+ and Cl- in the ice VII structure following this model
requires only average local distortions of 0.2-0.3 , i.e. displacements in agreement with the
measured Debye-Waller factor. The presence of Li+ and Cl- ions apparently prevents a longrange ordering of the molecular orientation, that is, a transition to the hydrogen-ordered ice
VIII, when the sample is cooled. This is not surprising given the strong electrostatic interactions
involved.
Figure 9. Left: Visualization of the inclusion process from the amorphous matrix during T-annealing. Note the strong
influence on the orientation of the water molecules in the immediate neighbourhood of the ions. Right: Structure of
pure and salty ice VII. a) Ideal structure of ice VII with hydrogen in one possible instantaneous configuration, showing
the octahedral interstitial void. bd) Snapshots of three typical configurations in salty ice VII (LiCl6H2O) derived from
ab initio simulations, showing the local distortions caused by the incorporation of Li (yellow) and the Cl (green) at
interstitial and lattice sites.
Neutron diffraction does not allow to determine the position of Li+ and Cl- because both ions are
weak neutron scatterers and their concentration is relatively small. We thus validated the
146
proposed structure by ab-initio calculations. The calculations provided detailed insight into local
structural features, which are impossible to obtain by our high-pressure diffraction experiments.
Simulations were carried out on a box of 3 X 3 X 7 ice-VII-like cubic unit cells. From
simulations, the Cl- anions are found to replace water molecules, whereas the Li+ cations are
positioned between sites of the water molecule. Figure 9 shows three typical configurations (b-d)
extracted from our simulations and compare them to the respective cubic unit cell in the ideal
ice VII structure, with the hydrogen atoms at instantaneous positions. Interstitial incorporation
was known to occur for small neutral molecules such as H2 [Loveday08] or He [Kuhs88],
producing `stuffed ice', but not for ionic species. We expect that the incorporation of ions
significantly modifies the properties of ice VII. For example, owing to its interstitial position, the
Li+ cation is thought to be able to jump from site to site, resulting in ionic conduction. Moreover,
owing to the orientational disorder introduced by the ions (Figure 10), at high temperatures
water molecules are further believed to be able to rotate around their center of mass, resulting in
what is known as a plastic solid [Vega09].
Figure 10. Spatial distribution of H2O dipole moment in pure ice VII (left) and LiCl6H2O ice VII (right) from MD
simulations.
Having observed the existence of LiCl6H2O ice VII, one might speculate about the existence of
other LiCl-hydrates based on the various other high-pressure ice phases. This is indeed likely
because their densities are lower, which makes incorporation of ions easier, especially for salts
with larger ionic radii. Ice VI is, for example, a good candidate for salt incorporation.
Experimental evidence for the incorporation of small amounts (2 mol%) of NaCl into ice VII by
compression of the salty liquid has indeed been proposed by [Frank06,Frank13], even if the
suggested lattice contraction under salt inclusion seems unrealistic. However, proven the
existence of LiCl-ice VII, it is also conceivable that ice VII with a very high salt content could be
produced starting from an amorphous NaCl-water mixture. The existence of NaCl-ice VII would
be still more relevant due to the major role of this salt in nature. We recently tested this
hypothesis during a new experiment on PEARL, ISIS [LudlPCCP16]. We obtained some
preliminary data indicating that NaCl-ice VII can be formed by annealing NaCl-VHDA at
pressures higher than those necessary for LiCl. Using the same argument employed to unravel
the LiCl-ice VII structure, based essentially on the known structure of the amorphous precursor
and on the measured lattice expansion, we believe that Na+ ion may be included in the ice VII
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lattice by occupying a substitutional site, as Cl-, and thus occupying the center of the bcc cube
and not one of its faces as Li+ (Figure 11). This would reduce the lattice expansion and the
distortion of the water molecules position with respect to an interstitial position. However, this
inclusion mechanism probably requires higher pressures then those applied, in order to increase
the number of 8-fold coordinated ions in the amorphous precursor, which most likely gives rise
to crystallization into the substitutional ice VII. Further experimental investigations are needed
to corroborate this hypothesis, as well as the stability of the proposed Na+ and Cl- substitutional
structure needs to be tested by ab-initio simulations.
Figure 11. Na+ ion in a 8-fold configuration in the salty-VHDA solid (left) and in the salty ice VII crystal (right).
Salty ice at Mbar pressures: HB symmetrization
The richness of the phase diagram of water reduces drastically at very high pressures where only
two molecular phases are known, i.e. proton disordered ice VII and proton ordered ice VIII
[Finney_review] (see Introduction). In these two phases the hydrogen bonds are characterized by
a pronounced double-well proton transfer potential. Calculations show that upon reducing the
distance between donor and acceptor oxygens, the proton potential degenerates into a singlewell potential [Marx05], giving rise to a symmetric or centered hydrogen bond, where hydrogen
atoms are located midway between two neighboring oxygen atoms. Infrared (IR), Raman and
more recently synchrotron radiation measurements
[Gonchy99,Loubeyre99,Aoki96,Sugimura08] have provided evidence for the transition in water
from the molecular proton disordered ice VII to an atomic phase with symmetric hydrogen
bonds when the distance between acceptor and donor oxygen atoms decreases below 2.3
Angstrom (at about 60 GPa). As mentioned in the introduction, quantum effects play an
essential role in the phenomenon of hydrogen bond centering: first-principle calculations predict
an intricate pre-transitional behaviour, characterized by possible intermediate disordered ice X
or VII phases [Stillinger84,Marx05,Parrinello96,Parrinello98,Caracas08]. At room temperature,
this transition is described as a change from a frozen-in static disorder to a dynamical disorder
mainly induced by proton hopping along hydrogen bonds, via transient ionic defects [Marx05].
However, though it is well known that the number of ionic defects in ice can be remarkably
increased by salts dissolution in water [Klime13], the effect of dissolved ions on the ice VII to
ice X transition has never been investigated.
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Figure 12. Pressure-temperature phase diagram of LiCl ice as sketched from our previous neutron diffraction
experiments and MD simulations [BoveNatMat09, BovePRL11, LudlPCCP15, LudlPCCP16]. Specific thermodynamics
paths have been followed for R=6 and 13 solutions (1) and for R=30 and 50 solutions (2) in order to first produce the
amorphous precursor embedding the salt and then crystallize salty ice under pressure. The shadowed part is the region
of existence of the polyamophic s-HDA and s-VHDA phases.
Having observed that high pressure water polymorphs can contain substantial amounts of ions
[BoveNatMat,LudlPCCP2016] in ion-filled ice structures, the question arises if these structures
are stable up to very high pressures, as observed for stuffed ices [Kuhs88,Loveday08, Lokshin04],
and how the presence of ions affects the transition to the high-pressure symmetric phase. These
questions cannot be answered (yet) by neutron diffraction studies, due to pressure limitations of
this technique.
We performed Raman studies in Diamond Anvil Cells (DAC) up to Megabar pressures of LiClices. Due to its high vitrification ability, LiCl-water represents the ideal system to produce the
salty-VHDA phases serving as precursors for producing the salty-ice VII crystals at different salt
concentrations. The explored pressure range, 1-150 GPa, covers the stability fields of ice VII, ice
VIII and ice X phases in pure water. Raman spectroscopy coupled with the diamond anvil cell
technique is ideal for probing Hydrogen bond symmetrization. In particular, the observation of a
single O-O vibrational mode of T2g symmetry in the low frequency range
[Gonchy99,Loubeyre99] is commonly used to identify the transition to the cuprite-type
structure of ice X. A sketch of the high-pressure phase diagram of salty LiCl water as obtained
from our studies [BoveNatMat,LudlPCCP15,Ludl PCCP16] is represented in Figure 12, where
the thermodynamic paths followed in the our experiments are also indicated.
Salty ice VII samples LiCl:RH2O, at different salt concentrations, namely R=6, 12, 30, and R=50
were prepared following the procedure detailed in [BoveNatMat09]. In particular, R=6 aqueous
solutions were directly loaded into high-pressure chambers of 30 to 40 micrometer in diameter
in a rhenium gasket between two type IIa synthetic diamonds mounted on a symmetric Mao-Bell
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type cell. A salt-doped amorphous sample was produced by fast quenching (104 K/s) of a R=12
aqueous solution as in [LudlPCCP15], loaded under liquid nitrogen, compressed to 5 GPa, and
then annealed at this pressure, in order to promote salt inclusion in the ice lattice. Finally R=30
and R=50 LiCl aqueous solutions were loaded in the cell at ambient temperature into goldcoated high-pressure chambers of 10 micrometers in diameter, compressed to 5 GPa, warmed at
400 C to achieve the liquid state, and then very fast quenched (cooling rate >105 K/s) to 77 K by
directly immersing the cell into liquid nitrogen. In such a way we obtained an amorphous s-HDA
phase (see previous section), which was transformed under annealing at 5 GPa to the s-VHDA.
When annealed at 320 K at 5 GPa, this s-VHDA transformed into the LiCl ice VII structure. The
three OH-stretching modes appear thus distinct in the Raman spectra, even if still broadened by
the increased disorder in the structure introduced by the salt [BovePNAS15].
The softening of the OH stretching modes with pressure (Figure 13) and the appearance of the
characteristic ice X O-O T2g mode (Figure 14) have been measured at high resolution and
compared with a pure H2O sample. The high-frequency OH stretching vibrations in H2O ice VII
form a disorder-broadened triplet, assigned to 1 (A1g), 3 (Eg ), and 1(B1g) modes in order of
increasing frequency. As in [Gonchy99, Loubeyre99, Aoki96] we observe a softening of these
modes with pressure, signaling the approach of a displacive phase transition. In particular, the
high-frequency 1 (A1g) band has the largest pressure shift in pure water and its softening has
been directly linked to the appearance of the ice VII to ice X transition at higher pressures. It can
be readily observed from Figure 13 that the softening of these bands is strongly reduced by the
presence of salt.
Figure 13. Raman frequencies of the
(A1g ),
(Eg ), and 1 (B1g ) modes as a function of pressure in pure H2O compared
to LiCl 12 H2O up to 40 GPa. For higher pressures, the triplet strongly decreases in intensity. The pressure dependence
of the O-H stretch Raman bands in pure ice VII is in agreement with previous high-pressure Raman measurements
[Gonchy99, Loubeyre99, Aoki96]. Solid lines are guides to the eye. The insert shows a simulation snapshot of salty ice
VII structure, where the Cl ion substituting a water molecule is represented in blue and the interstitial Li ion in pink.
Further increase of pressure to about 80 GPa results in the appearing of a new, narrow band in
the low-frequency spectrum at about 900 cm-1, attributed to the O-O stretching mode in the
symmetric ice X phase [Gonchy99, Loubeyre99, Aoki96] (Figure 18). The frequency of this new
excitation increases with pressure and the corresponding peak is the only first-order excitation
150
in pure H2O at these pressures, due to symmetry restrictions. As shown in Figure 46, the
appearance of this band is pushed to higher pressures (namely at about 90, 100 GPa and 120
GPa for R=50, 30 and 12 solutions respectively) in the presence of salt inclusion. Furthermore,
the presence of the O-O stretching mode was not observed in the R=6 salt solutions up to the
maximum investigated pressure of about P=150 GPa (1.5 Mbar).
Figure 14. High resolution Raman scattering measurements in the 300-1000 cm-1 range as function of pressure up to 150
GPa for R=50 (right top panel), R=30 (left panel) and R=6 (right bottom panel) water molecules for LiCl. Numbers
indicate the nominal pressure in GPa. The transition from ice VII to ice X phase is observed by the appearing of the T2g
O vibrational mode, visible at high pressure in the 900-1000 cm-1.
Figure 15 shows the main result of our study: the inclusion of ions pushes the ice-VII to ice-X to
higher and higher pressures, and this occurs with a nearly exponential law, with a similar trend
observed both from experiment and simulations. The shift of almost 35 GPa between the abinitio calculations and the experimental transition, defined by the appearance of the T2g Raman
mode, is mainly due to the fact that nuclei are approximated as classical particles in our
molecular dynamics calculations, and are therefore unable to tunnel through the potential
barrier [Bronstein14]. A deeper atomic-level analysis reveals that the bond symmetrization is
indeed hindered by the ions, particularly in the first neighbor shell of an ionic intrusion (see inset
Figure 15). Similar experimental results have been obtained for NaCl solutions close to the
eutectic composition (R=11.5) where, again, no T2g mode has been observed up to 1.5 Mbar
pressure, and a similar shift in pressure transition has been observed at low concentrations R=52
[BronsteinPRB15].
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Figure 15. The Ice VII to Ice X transition pressure dependence with salt concentration in LiCl:RH2O solutions: Raman
scattering experiments (green dots), calculations by ab-initio simulations (red dots) . The green cross represents the
maximum pressure value reached for the LiCl6H2O sample where the transition has not been observed. Simulation
snapshots of the ice X phase in pure water and LiCl20H2O are shown.
We attribute this effect to the strong perturbation introduced by the dipolar electric field
generated by the charged ions. However, since the quantum nature of protons is a key in the case
of pure ice VII to ice X transition, this raises the question of whether or not the shift of the
transition pressure is associated with a strong decrease of the quantum aspects of hydrogen,
namely proton tunneling and zero-point energy, under the presence of the ions dipolar electric
field [BronsteinPRB15]. Finally we want to stress that the observed salty ice structures seem to
be stable up to very high pressures, as the changes observed in the Raman spectra are continuous
up to the observe salty-ice VII to salty-ice X transition, proportional to the initial salt content,
and consistent with a gradual transformation of the salty-ice VII crystal into the symmetric saltyice X phase. The stability of this phase under high temperature remains to be addressed. This is a
relevant point, as Ice X is thought to be the precursor for a superionic ice phase [Cavazzoni99,
Militzer13], which would manifest itself in the pressure range of ice X but at higher
temperatures. This superionic phase is a non-molecular phase characterized by mobile
delocalized hydrogen atoms moving in the oxygen lattice and giving rise to electrical conduction.
This ice phase is thought to be the dominant phase of the interior of giant icy planets and may be
responsible for the observed anomalous magnetic moment of Uranus and Neptune. Recent
studies showed experimental evidence for superionic conduction at significantly low
temperature compared with earlier theoretical estimates [Ninet12, Ninet13, Dubrovinsky12].
The presence of salt impurities in natural ice, incorporated via oceanice interaction, rockice
interaction at depth, or processes that occurred during accretion [Anderson98, Schilling04,
Khurana98], could strongly modify the thermodynamic conditions and the mechanism for the
appearance of such extreme states of matter. Furthermore, salt promotes novel exotic properties,
thus challenging our present description of the physics of these bodies, essentially based on the
assumption of the properties of pure ice under high pressure. We believe that the study of ionic
152
impurity effects on the onset of superionicity and of the high-pressure phases predicted in ice
beg for a systematic investigation.
Ice clathrates under pressure
At ambient and moderate pressures (P<0.5 GPa) all gas hydrates adopt clathrate structures
[Mao02], i.e. structures where the gas molecules are trapped in Hydrogen-bonded H2O
frameworks (cages) [Sloan97, Vos93, Loveday01, Loveday08, Mao02, Mao07].
The cage topologies of hydrate clathrates are identical to fullerenes - in which the cages are
isolated- and similar to cages found in certain zeolithes which are however formed by a
covalently bonded (Si,Al)-O framework which is stable on its own without the inclusion of guest
molecules (Figure 16).
Figure 16. Left : The structure of cubic structure I (CS-I) clathrate hydrate. Right : The structure of cubic structure II
(CS-II) clathrate hydrate viewed along a cubic [011] direction. The red balls represent the O atoms of the host water
molecules and the black balls mark the centres of the guest molecules. For clarity the H atoms have been omitted. The
crystallographic axes a and b are shown.
The natural occurrence of methane gas hydrate in permafrost area or ocean shelves in large
quantities, the risk due to their formation in oil and gas pipeline, as well as their potential
utilization for gas transportation in soft conditions (i.e., close to atmospheric pressure and room
temperature) makes methane clathrate hydrates particularly interesting and fascinating for
energy and environmental applications. Furthermore, since it is believed to have been the
dominant methane-bearing phase in the nebula from which the outer planets and satellites
formed, the properties of methane hydrate are crucial to models of bodies in the outer solar
system.
Hydrogen clathrates also represents a potential means to store hydrogen to be used for energy
applications, as they show an exceptionally high H2/H2O ratio (1:2), thus hydrogen clathrate can
trap hydrogen at mass fractions rivalling those of the best materials for hydrogen storage. These
clathrates are formed under pressures of the order of few kbars but can be recovered at the
normal atmospheric pressure where they remain stable as long as the temperature is below 150
K. In these conditions they can reversibly store and release molecular hydrogen at a mass
153
fractions of up to 3.77 percent. These properties could lead to a hydrogen storage system that
could figure prominently in a hydrogen economy. But to develop such a system requires a detailed
understanding of how hydrogen clathrate traps molecular hydrogen at various pressures and
temperatures. The ongoing research of the hydrogen storage in clathrates explores the
moderately low (77-300 K) to moderately high (300-600 K) temperature range to search for new
compounds capable of retaining a significant amount of hydrogen. Because of these important
properties and applications, clathrate hydrates have long been extensively studied and explored
in the relatively low-pressure range (00.5 GPa).
Their cage topologies have been determined by X-ray and neutron diffraction studies, and the
vibration and rotational spectra of the guest molecules have been characterized by Raman,
infrared and NMR techniques [Sloan97, Vos93, Loveday01, Loveday08, Mao02, Mao07].
The clathrates structures are topological duals of Frank-Kasper crystals (also experienced by
metal alloys and zeolites), namely tetrahedrally close-packed structures made of five polyhedral
cages (ordered by increasing cavity size): dodecahedra (512), irregular dodecahedra (435663),
tetrakaidecahedra (51262), hexakaidecahedra (51264) and icosahedra (51268). If there is in principle
an infinite number of Frank-Kasper crystals, only four Frank-Kasper structures have been
observed in clathrate hydrates : sI, sII, sT and sH (with sI and sII being by far the more common
ones at moderate pressures and sH the more common one at high pressures, see Figure 17 for
the building principle). The unit cell of sI consists of 46 water molecules forming 2 512 and 6 51262
cages, thus the water to guest ratio is 5.75 in case of full occupancy of the two types of cages. The
unit cell of sII contains 136 water molecules forming 16 512 and 8 51264 cages, implying a water to
guest ratio of 5.67 in case of full occupancy. In practice, typical occupancies of large cavities
(51262 and 51264) are greater than 95%, while occupancy of small cavities (512) vary widely
depending on the guest composition, temperature, and pressure. This variation causes clathrate
hydrates to be called nonstoichiometric. In the case of hydrogen hydrate, sII hydrate is formed
with multiply occupied large 51264 cages, whose occupancy was found to vary from two to four
over the temperature range of around 200 to 40 K [Lokshin04]. The unit cell of sH contains 34
water molecules forming 3 512, 2 435663 and 1 51268. If the small cages (512 and 435663) contain each
one guest, the number of guests in the large cages (51268) is the source of considerable discussion
[Loveday08] and is most likely to vary between two and five depending on the pressure and the
guest size. In the case of methane hydrate, Loveday and co-workers [Loveday01] reported a
water to guest ratio of 3.5 for the structure H.
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Figure 17. Building principle of the common clathrate hydrates structure I (sI), structure II (sII) and structure H (sH).
All these structures are built from differently sized nanocages. For example, the notation 51262 refers to a nanocage
consisting of twelve water-pentagons and two water- hexagons. The numbers on the arrows refer to the numbers of such
nanocages contained in the unit cell of the individual structures. The 3 possible nanocages are also represented below.
The vibrating guest molecule is the essential ingredient for the cage stability of clathrates. In fact,
the elasticity of the H-bonded cages introduces additional degrees of freedom that allow for the
coupling of guest and host vibrations. This coupling does not only influence the motion of the
confined guest particle but equally prevents the cage from collapsing.
Therefore, the access to the guest dynamics provides a basis for an understanding of specific
guest induced host-lattice rearrangements (figure 18).
Figure 18. Structural view of the thermal variation of the D2 distribution in the large (64512 hexakaidecahedron, top),
and small (512dodecahedron, bottom) cages in D2-clathrate. Oxygen atoms are shown as red spheres, deuterium
framework atomsgreen, and guest D2 moleculesyellow. Below 50 K, the guest D2 molecules are localized: in the large
cage four molecules are oriented to the centers of hexagons yielding a tetrahedral cluster; in the small cage one D2
molecule is statistically distributed over 20 positions oriented towards the oxygen atoms forming the dodecahedron.
155
With increasing temperature, the D2 molecule can more freely rotate, yielding a nearly spherical density distribution
inside the cages (right).
Similarly to the case of salty ices, until recently the expectationbased mainly on calculations
was that all ice clathrates were dissociated into ice and gas by the application of relatively modest
pressures (~1 GPa). However, over the past ten years, new experimental studies have shown
[Loveday08, Mao02, Mao07] that this view was incorrect. All the systems so far studied undergo
structural rearrangements to other, new types of hydrate structures that remain stable up to
much higher pressures than had been thought before, forming structures already recognized in
the late 80s as stuffed ices [Kuhs88, Kuhs92] (Figure 19). The latters (whose water networks are
closely related to that of ice Ih, II or Ic) present water to guest ratios as low as 1.
These high-pressure clathrates can be present in the outer solar system (comets, satellites of the
gas giant planets, Mars), binding guest molecules at fairly high temperatures; this could play a
major role in the explanation of the punctual gas (like methane) abundances detected by space
probes [Moussis08]. Because of these important properties and of their potential applications,
clathrate hydrates have long been extensively studied and explored in the relatively low-pressure
range (00.5 GPa). However, due to the lack of adapted investigation techniques, their dense
phases remain poorly characterized. Moreover, much could be learned about water-water
interactions in these topologically rather complex systems, especially if one could follow the
pressure dependence of the host structure over a wide pressure range. Likewise, much could be
learned about the guest-host interactions in a wide range of guest species, from noble gas atoms
to large (and polar) organic molecules.
Figure 19 Structure of hydrogen clathrate as derived from ab initio variable-composition evolutionary simulations by
[Qian14]. a) Ih-C0 structure at 0.5GPa, (b) C3 dense filled ice structure at 30GPa. Large red and small blue spheres are
O and H atoms in water molecules, respectively; the yellow spheres represent the H2 molecules Red dashed lines
represent hydrogen bonds.
The microscopic mechanism determining clathrate destabilisation under high-pressure can be

investigated by directly probing the guest gas molecules diffusion, the rattling and jump
mechanisms in/from/out of the cage. The water molecule framework can be easily selectively
deuterated, in order to minimize its background contribution that shows up as an elastic line in
156
the measured QENS (Quasi-elastic neutron scattering) spectra [BovePRL13], and to ease the
extraction of information on the guest molecule dynamics. Both diffusive and fast relaxation
motions can thus be measured on a time scale which is typically of the order of one to hundreds
of ps. Furthermore, analysing the dynamics of the guest molecules encapsulated within water
cages leads to the exploration of the potential energy surface as seen from the guest molecule
inside the cage. By applying pressure, the distances between the guest molecule and the cage can
vary substantially as an example the OC distance varies by more than 20 % in the clathrate
methane for a pressure variation of 3 GPa- thus allowing to derive very valuable information on
the potential energy surface as a function of varying distance.
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158
Synchrotron and neutron studies in planetary science
Helen
Maynard-Casely,
Australian
Nuclear
Science and
Technology Organisation
Synchrotron
and neutron
studies
in planetary
science
email: helen.maynard-casely@ansto.gov.au
Helen Maynard-Casely
twitter:
@Helen_E_MC
Australian Nuclear Science and Technology Organisation, Kirrawee, NSW, Australia
helenmc@ansto.gov.au
twitter: @Helen_E_MC
Abstract
The study of planetary interiors provides a fertile ground directing high-pressure experiments,
and synchrotron and neutron experiments have been key to our understanding of these diverse
bodies. In these lecture notes I will outline what observational constraints have placed on our
knowledge of these planet interiors, then summarise the conditions as they are currently
understood. I will then detail an instrument currently used for investigating planetary interiors
before detailing how such studies have enhanced our knowledge on the interior of Saturns
moon Titan.
Keywords
Planet interiors, sample environment, complex, instruments, seismic, magnetic fields, gravity,
structures, equations of state, transport properties.
Introduction
The deepest hole ever dug by humankind on the Earth is the Kola Superdeep borehole 1, where a
bore 12,262 meters was drilled into the crust. Thats nearly 13 km, so what about the other
(roughly) 6,368 km? Of course, as you all know, the best way to study materials under these
conditions is with in situ investigations and crystallography is a particularly powerful tool for
this. But rather than focus on the Earth, remember that theres quite a bit of more mass in the
solar system to be investigated. Jupiter, for instance, is 395 times more massive than Earth and
with ~99 % of the mass of this gas giant existing under more than 1 GPa of pressure theres a lot
of work to be done!
Figure 1. The relative scale of the planets in our solar system image from
http://www.lesud.com/lesud-astronomy_pageid81.html.
159
Re-creating the conditions of planetary interiors is challenging, often requiring both extremes of
pressure and temperature. However, realising the structure of materials with such experiments
can have planet-sized implications. To undertake these crystallographic experiments requires
high-flux instruments, usually located at x-ray synchrotron and neutron facilities.
In these notes I will first outline how we know what conditions to target in the pursuit of
knowledge on planetary interiors (Ill be trying to spend less time on the Earth, as other lectures
will cover that!). Then I will outline some of the information that can be gleamed from
crystallographic experiments that can enhance our knowledges of planetary interiors, as well as
an instrument that can undertake these measurements. Ill round it off with a case study of
where neutron crystallographic studies have made impact in our understanding of planetary
interiors.
How do we know about planetary interiors?
If we have only dug a hole 12.3 km deep on the Earth, and we havent really progressed with
digging holes on other planets (the largest extra-terrestrial hole is that left behind is deep impact
on the comet Tempel 1), how do we know anything about the conditions below the surface?
Seismic investigations
Seismic investigations have proved the best way to sample the interior of a planetary body and it
is to these measurements that we owe our understanding of the Earths interior structure.
Variations in velocity of the longitudinal and transverse waves probe both the density and state
of the materials the seismic signals travel through 2. However, to date the only other planetary
body that we have significant seismic data from is the Moon. This is courtesy of the Apollo
program which first experimented with a single station during Apollo 1, before installing a
network of four stations in later missions 3. Though this network was limited by the fact all of the
instruments were located on one hemisphere, stable velocities for the upper mantle were
determined and concluded that the crust of the Moon was thinner (35-45 km) than previously
thought 4. Subsequent analysis of the Apollo seismic data has now also suggested that the moon
has part-liquid core 5, like on Earth.
Seismic investigations on other planetary bodies in our solar system have been rather stunted to
date, with a number planned and then scrapped due to funding. The next highlight will be
NASAs InSight mission to Mars, which will carry two seismic instruments 6. These coupled
with heat flow and reflex measurements, means that InSight will be the first dedicated
geophysical mission on another planet. Additionally, the field of helioseismology is increasingly
being applied in probing the interior structure of the Gas Giant planets 7. These have centered
about the search for oscillations in various spectroscopic observations, but had to wait until 2011
for the first strong (above signal-to-noise) detection of such features. Recent observations of
Neptune and Uranus by NASAs Kepler K2 mission 8 will also test the ability of these
measurement to reveal details of the interior structures.
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Heat flow measurements

On the terrestrial and dwarf planets, observations of heat flow usually only have local subsurface
(rather than global) implications. Examples of these observations are the high heat flow
observed from Saturns moon Enceladus Tiger Stripes 9 and the search for volcanic activity on
Venus 10. However, unlike the terrestrial planets, the giant planets have a large intrinsic heat
flow that can be measured from long-range remote sensing. This is because of both the larger
values of heat flow these planets exhibit and lower background, being further from the sun.
Table 2.1 gives the observed heat ow parameters for each of the giant planets. Comparing the
internal power per unit mass (parameter 4, Table 1) to the value from a carbonaceous chondrite
[0.4 x 1011 W kg-1] (taken to be characteristic of radioactive decay) we see that Neptune's heat
flow is too large to be described by this process alone. Current models suggest that the large
internal heat flux from the giant planets is primarily a remnant from the accretion process 11.
The internal power per unit mass of Neptune is in stark contrast to the value exhibited by
Uranus, which is particularly low. This has been interpreted to show that the remnant heat of
Uranus is trapped beneath a non-conductive layer 12.
Table 1. Heat flow parameters for the gas giant planets, with values taken from Hubbard et al. 13. The effective
temperature is the total infrared energy flux from the planet including the contribution from sunlight. The energy
balance is the ratio of the infrared energy flux to the value for thermalised sunlight alone. The average internal energy
flux is the total value from each planets interior, with the last parameter being the average of this per unit mass.
Parameter
Jupiter
Saturn
Uranus
Neptune
(1) Effective temperature (K)
124.4(3)
95.0(4)
59.1(3)
59.3(8)
(2) Energy balance
1.67(9)
1.78(9)
1.06(8)
2.61(28)
(3) Internal energy flux (Wm-2)
5.44(43)
2.01(14)
0.042(47)
0.433(46)
17.6(14)
15.2(11)
0.39(44)
3.22(34)
(4) Internal power/unit mass (10 Wkg )

11
-1
Gravity
The gravity field of a symmetric and spherical planet only reveals one piece of information: the
body's mass. However, fortunately for planetary science, all of the planets rotate and
consequently oblate in a way which is constrained by their interiors. Additionally, for the
terrestrial planets, local gravity anomalies can be observed through the acceleration and
deceleration of spacecraft orbiting them. Recent highlights of this sort of measurement has been
the detection of an ocean under the ice crust of Enceladus 14, as well as the detailed gravity map
of the Moon constructed from NASAs GRAILs spacecrafts measurements 15.
However, to probe the deep interior of a planet with gravity requires knowledge of the
gravitational moments which can be calculated from observations. They can be derived from the
orbits of both natural satellites and directly by artificial satellites. The gravitational moments
characterise the density distribution within a planet. These values have, for instance, been used
to constrain models of the gas giant planet interiors.
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In the case of Neptune and Uranus, from the observed J2 and J4 components, a common three
layer model has been constructed, a gaseous/fluid outer layer, overlying a large hot ice mantle
before reaching a dense core. The density profiles that fit the observational constraints in
Errore. L'origine riferimento non stata trovata. are shown in Figure 2. The value of J4 is
thought to require a central core of an Earth mass, accompanied by an atmospheric

enhancement in volatiles of about 20 times the solar values 16. Alternatively, though, a single
layer interior of a mixture of hydrogen, helium and rock mixture does fit the gravitational
moments. But, other gathered observations, such as the 30 times enrichment of methane in the
Neptune and Uranus atmospheres and their magnetic fields, further suggesting the existence of a
hot ice layer 13.
Figure 2. Comparison of four model density profiles which fit the observed gravitational moments for Neptune and one
for Uranus (light dashed line) taken from Hubbard and McFarlane 11. With the exception of the solid line (representing a
core-less profile of Neptune 16) all of these profiles exhibit the same three layers a gaseous/fluid outer layer, overlying a
large hot ice mantle with a dense core. However, the location of the transitions between these differs considerably
between the models.
Magnetic fields
Planetary magnetic fields are generated in the deep interiors and hence additionally place
constraints on our understanding of them. For instance, the fact that Mars has only a weak
magnetic field, points to the red planet having no internal dynamo - like that generated between
the liquid outer core and solid inner core on Earth.
162
Figure 3. The anomalous magnetic fields of Uranus and Neptune. The yellow lines indicated the magnetic field lines and
the grey dashed lines indicate the equator (perpendicular to the rotation axis) of each planet. Unlike the other planets in
the solar system with magnetic fields, their rotation axes and magnetic axes have an abnormally large angular separation,
and the magnetic field has a non-centred dipole.
Considering the magnetic fields of Uranus and Neptune, both of these bodies exhibit magnetic
fields that are anomalous to those observed elsewhere in the solar system, Figure 3. Unlike the
magnetic fields of Earth, Jupiter and Saturn; Uranus and Neptune's are not dipolar or axial
symmetric. It was suggested 13 that to generate fields of this nature a type of thin-shell dynamo
would need to arise. Calculations have shown that this is possible 17 but for this to occur a
convective region in the interior must arise. This is at odds to models previously introduced in
Figure 2, which assumed purely conductive interiors for Uranus and Neptune. Added to this,
the stark differences between Uranus and Neptune's heat flow was thought to arise from small
differences in their interior stratification 12. So whilst the previous models explain the presentday luminosity - they imply that the interiors would be stratified compositionally and unable to
undergo convection that is needed to generate the observed magnetic fields!
Summary of conditions to be investigated
The last point exemplifies why we need detailed knowledge of how the materials contained
within all our planetary bodies. For instance, to properly model the hot ice layer within Uranus
and Neptune - the structure, physical, transport and even electrical properties of water,
ammonia and methane must be accurately constrained. Piecing together the observational
constraints we now have the following pictures of interior conditions with planetary bodies:
Terrestrial planets in our solar system are Mercury, Venus, Earth and Mars. Conditions
within their interiors range from 0 - 360 GPa and 300 6800 K.
Gas Giant planets Our solar system may not be unique in containing gas giant planets
however, we estimate the interior conditions of Jupiter, Saturn, Neptune and Uranus to range
from 0 1,000 GPa and 20 35,000 K.
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Dwarf planets a relatively new category of planet, which covers the icy moons of the gas giant
planets, asteroids and Kuiper belt objects. Conditions can range from 0 5 GPa and 40 1700
K with the extremes defined by the biggest body in this class Jupiters moon Ganymede.
What do we need to know?
Structures
No matter how good DFT calculations are, a structure is needed to start to understand the
nature of materials under the extremes of planetary interiors. This need is furthered by the
shear range of polymorphism that many key planetary materials exhibit in the
pressure/temperature ranges cited in the previous section. The development of high-pressure
single crystal data collection, particularly at synchrotron sources 18 (plus see M. McMahons
lecture) has very much accelerated the ability to determine complex structures under these
extreme conditions. This has been a fantastic tool for resolving keys issues with Earth minerals,
for instance investigating high-pressure polymorphs of calcium carbonate 19 (a possible store of
carbon in the deep earth) but has yet to be applied in earnest to other planetary problems. Of
course, it isnt always necessary to grow a single crystal to find the structure of high-pressure
phases the fantastic resolution on offer from synchrotron and time-of-flight neutron sources
means that complex structures can still be resolved from in-situ powder diffraction data.
Equations of State
Following on from structural information, understanding how the structures respond to
pressures and temperatures is the next stage in applying this fundamental knowledge of
planetary interiors. As you will recall from R. Angels lecture, for most materials pressure is of a
greater effect that temperature so the most general approach is to start with an isothermal
equation of state and apply a thermal expansion correction to this. Those these effects can be
calculated - in determining equation of states for planetary materials, synchrotron sources are
particularly key given their high-resolution for resolving small shifts, as well as anisotropic
effects with pressure and temperature.
Combining equations of state of multiple planetary materials enables the building of a whole
planet models, able to chart density variations through the planet. Perhaps the most successful
of these in the Preliminary reference Earth model 20, which has recently been extended so that it
can be applied to Earth-sized exoplanets 21. Of course, most of the planetary bodies in our solar
system are not made of silicates; currently the building of a similar all-encompassing reference
model for icy moons objects is impinged by the lack of understanding of hydrates and hydrated
silicates under pressure.
Transport properties
Materials can be very complex in their response to pressures and temperatures, and knowing
how atoms within them transport through their structures is vital in understanding energy
transport within the interiors. Many of these types of measurement investigation of vacancies
164
and impurities within planetary materials are very challenging in situ (for more details see S.
Pascarellis lecture) but planetary studies have benefited from ex-situ measurements with
fluorescence and spectroscopy techniques available at central facilities. Where exciting
developments are still to be seen in this area, is in application of tomographic data collections to
in situ samples.
Magnetic/Electric properties
Neutron scattering is the best tool for probing magnetic structures however to date studies
utilising this and applying to planetary interior issues has been limited. A particular focus in this
area has been into the high spin/low spin state of iron in Earth minerals 22, usually observed with
spectroscopic techniques. Of future interest though, will be how low-z materials like methane,
ammonia and water, can interact at extremes to produce magnetic fields of the gas giant planets.
What instruments are out there?
There are multiple synchrotron and neutron central facility instruments that have carried out
experiments that probe the interiors of planets. Given that you will hear about many of these
instruments during the course, I will only highlight one the PLANET (BM-11) instrument
located at the Materials and Life science facility (MLF) within the Japanese Proton accelerator
research complex (J-PARC).
PLANET 23 is a neutron time-of-flight diffraction instrument which has been optimized for use
with a number of high-pressure apparatus, principally through a 6-axis press "ATSUHIME" able
to achieve sample pressure of 20 GPa and temperature of 2000 K. A particularly important part
of the optimisation of the instrument has been the incident slits and receiving collimation that
allows parasitic scattering from the high-pressure cells to be eliminated. This is especially
important for the study of liquid and amorphous materials (see C. Sanloups lecture for more
information). Though a relatively new instrument (commissioned in 2012) they have already
had success in determining the site occupancy of interstitial deuterium within iron 24 a key
observation for determining the composition of the Earths (and other planets) metal cores.
Figure 4. High-pressure presses and PT range currently available at PLANET, taken from Hattori et al.
23
165
Figure 4 shows the range of temperatures/pressures that apparatus on the PLANET instrument
can access. But virtue of it being a neutron diffractometer, the PLANET instrument is
particularly effective for the study of hydrates and the application of these results to the
interiors of icy moons. The high-resolution diffraction data that the time-of-flight technique
means that not only can it track details of interstial atoms (as the above example) but complex
crystal structure can be solved too. Such as the example show by Figure 5 below.
Figure 5. A mixture of deuterated sulfuric acid hydrate and water at 280 K and 2.5 GPa, which has formed a new hydrate
observed by the PLANET instrument. The high-resolution enables powder data has enabled the realisation of this
structure (inset) which would be a stable phase within the interiors of Jupiters moons Europa and Ganymede.
Case study: Methane on Titan
High-pressure crystallographic studies can have significant implications for the understanding of
the interiors of planetary bodies. This has been the case for Titan, the largest moon of Saturn.
Like other satellites within the region it has a low overall density (1.88 gcm-3), indicating a large
compositional fraction of water. Its position within the solar system also dictated that a suite of
light molecular materials, such as ammonia and methane hydrates, would have initially formed
the moon's interior 25. Titan has a substantial atmosphere a unique feature among the moons of
the solar system and like our own atmosphere it is mainly composed of nitrogen, but contains up
to 5% methane 26. This relative high percentage of methane presented a challenge. The photochemistry of the stratosphere of Titan is such that
the present amount of methane would be removed within a few million years 27. The
implications of this were that the atmospheric methane must be being replenished.
166
Figure 6 . Illustrating a model of the interior evolution of Titan 25 before the discovery of MHIII. (a) shows the interior of
Titan just after accretion, with a rocky carapace overlying a mixture of high-pressure ice and methane clathrate. As Titan
differentiated, with gradual warming and increase of pressure, the proto-core the methane hydrate dissociates resulting
in (b), with a layer of free methane. The vastly more buoyant methane ruptures the rocky carapace, initiating core
overturn. As this methane is half as dense as the ammonia-water it rises rapidly to reach the atmosphere, (c).
Methane would have initially accreted into Titan in the form of methane hydrates, along with
ice, ammonia monohydrate and rock from the solar nebula 28. It is thought that the beginning
internal stratification resulted in a rocky carapace overlying a mixture of methane clathrates, ice
and ammonia hydrates, as shown in Figure 6.
The model presented in Figure 6 was built with the assumption that methane hydrate would
dissociate under moderate pressure. With this knowledge, the rising temperatures and pressures
of this proto-core would cause the methane clathrate to dissociate creating a layer of free
methane. The methane would rupture the overlying rocky carapace initiating core overturn (the
denser rock differentiating to the centre of the body). The free methane, which is half as dense as
the water and ammonia ocean, would release rapidly into the atmosphere. As already pointed
out, methane would only have a very limited life-span within Titan's atmosphere, being lost
because of gravitational or photo-chemistry effects. The original source of methane
replenishment was thought to be from oceans of simple hydrocarbons (methane, ethane) or
from a methane saturated regolith that would exist on the surface of the moon 25.
The realisation that solid methane hydrate persisted beyond 2 GPa had a profound effect on
models of the interior evolution of Titan. If methane did not dissociate before core overturn then
there would be no layer of free methane. Instead methane within the proto-core could exist as at
MHIII 29. Upon core overturn the MHIII could back transform to MH II and MH I - coexisting
with ammonia hydrates. A layer of methane hydrates up to 100 km thick would be present
within the interior. Tectonic and volcanic activity could provide a mechanism for the methane
hydrate to reach the surface and dissociate.
167
Figure 7. Current model of the internal evolution of Titan as described by Tobie et al. 30. Stage (a) is the same as in
Figure 6. As the methane clathrate would not have dissociated, the core overturn is a less dramatic process with the core
methane unable to escape towards the surface. This gradual process would result in episodes of methane outgassing
throughout Titans history. The first would result from the methane clathrate that could rise to the surface at core
overturn. This would come from the layer in (b) that is close to the surface and be relatively prolonged. The second
episode of outgassing would occur from the onset of convection within the silicate core. The core-methane hydrate
boundary would subsequently heat up and initiate dissociation, resulting in a subsequent rise to the surface. The third
occurs with onset of convection and crystallisation of an ice I layer just under the surface (c)
The current picture of Titan interior evolution is slightly more complex than originally set out
by Loveday et al. 29. Now widely accepted, the model of Tobie, Lunnie and Sotin 30 set out that
methane out-gassing into the atmosphere has been confined to three discrete periods in Titans
history. This model was constructed using both the high-pressure crystallographic information
on methane hydrate 16 and ammonia hydrate 31.
As summarised in Figure 7, the first methane out-gassing event occurs at core overturn with the
dissociation of methane hydrate forced to the surface as part of the overturning process. This
would result, as shown in Figure 7 (b), in a layer of methane hydrate close to the surface. As it is
exposed to the surface, the clathrate structure would decompose and release methane into the
atmosphere. The amount and rate of this out-gassing would be determined by the quantity of
methane hydrate within the proto-core. The second event would arise at the onset of convection
within the silicate core. This would warm the layer of methane hydrate at the core-mantle
boundary, Figure 7 (b) and cause it to dissociate. The methane could then rise through the
saturated ocean to the surface. Again this would be controlled by the initial amount of methane
hydrate, but also reflect the efficiency of convection within the silicate core. The third event, and
last according to the authors, occurs with the onset of convection and ice I crystallisation in
Titan's outer layers. Methane clathrate, still recumbent in the subsurface, is brought towards the
surface by icy plumes and would dissociate at ~1 km below the surface.
Future investigations
With the increasing number of exoplanets being discovered this is very much a growing area to
which high-pressure crystallography can be applied too. Of particular importance is the
168
investigation of hydrated silicates not just for understanding our own planet but also in
applying to the interiors of icy moons, such as Europa, Ganymede and Titan. And then, recent
observations 32 have shown that Pluto is far from being a cold dead world and its diverse surface
will be in part due to interior processes. It is also worth noting that Pluto is only one of a host of
Kuiper belt planetary bodies. Of course, as diverse as our solar system, the explosion in the
discovery of Exoplanets has confirmed the planetary science is only a growing business. Already
planetary modelling is, for instance, investigating topics such as the ability for super-Earths to
undergo planet tectonics 33, enabled in part by the understanding of high-pressure structures.
Lastly many questions still remain about the generation of magnetic fields by the gas giants.
Understanding the structure of matter at these extremes (>4 Mbar) of pressure will require most
of the techniques and developments being presented at the 49th Erice School!
References
1
2
3
4
5
6
7
8
9
Bodn, A. & Eriksson, K. G. Deep Drilling in Crystalline Bedrock: Volume 2: Review of Deep
Drilling Projects, Technology, Sciences and Prospects for the Future. (Springer Science & Business
Media, 2012).
Lognonn, P. Planetary seismology. Annu. Rev. Earth Planet. Sci. 33, 571-604 (2005).
Latham, G., Ewing, M., Press, F. & Sutton, G. The Apollo passive seismic experiment. SCIENCE
165, 241-250 (1969).
Chenet, H., Lognonn, P., Wieczorek, M. & Mizutani, H. Lateral variations of lunar crustal
thickness from the Apollo seismic data set. Earth Planet. Sci. Lett. 243, 1-14 (2006).
Weber, R. C., Lin, P.-Y., Garnero, E. J., Williams, Q. & Lognonn, P. Seismic Detection of the
Lunar Core. SCIENCE 331, 309-312, doi:10.1126/science.1199375 (2011).
Taylor, J., Teanby, N. A. & Wookey, J. Estimates of seismic activity in the Cerberus Fossae region
of Mars. Journal of Geophysical Research: Planets 118, 2570-2581, doi:10.1002/2013je004469
(2013).
Gaulme, P., Mosser, B., Schmider, F.-X. & Guillot, T. Seismology of Giant Planets. arXiv preprint
arXiv:1411.1740 (2014).
Barentsen, G. in American Astronomical Society Meeting Abstracts.
Howett, C., Spencer, J., Pearl, J. & Segura, M. High heat flow from Enceladus' south polar region
measured using 10600 cm 1 Cassini/CIRS data. Journal of Geophysical Research: Planets
(19912012) 116 (2011).
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11
12
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Shalygin, E. V. et al. Active volcanism on Venus in the Ganiki Chasma rift zone. Geophysical
Research Letters 42, 2015GL064088, doi:10.1002/2015gl064088 (2015).
Hubbard, W. B. & McFarlane, J. J. Structure and evolution of Uranus and Neptune. Journal of
Geophysical Research 85, 225 (1980).
Guillot, T. Condensation of methane ammonia and water in the inhibition of convection in giant
planets. Science 269, 1697 (1995).
Hubbard, W. B., Podolak, M. & Stevenson, D. J. 109 (Univerity of Arizona Press).
Iess, L. et al. The gravity field and interior structure of Enceladus. SCIENCE 344, 78-80 (2014).
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(GRAIL) mission. SCIENCE 339, 668-671 (2013).
Podolak, M., Reynolds, R. T. & Young, R. Post Voyager comparisons of the interiors of Uranus
and Neptune. Geophysical Research Letters 17, 1737 (1990).
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Stanley, S. & Bloxham, J. Convective-region geometry as the cause of Uranus' and Neptune's
18
McMahon, M. I., Loa, I., Stinton, G. W. & Lundegaard, L. F. Determining complex crystal
structures from high pressure single-crystal diffraction data collected on synchrotron sources.
unusual magnetic fields. Nature 428, 151 (2004).
High Pressure Research 33, 485-500, doi:10.1080/08957959.2013.831087 (2013).
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Merlini, M., Hanfland, M. & Crichton, W. CaCO 3-III and CaCO 3-VI, high-pressure polymorphs
of calcite: Possible host structures for carbon in the Earth's mantle. Earth Planet. Sci. Lett. 333,
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Planetary Interiors 25, 297-356 (1981).
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Letters 34 (2007).
170
Introduction to X-ray Magnetic Circular Dichroism
Introduction
to X-ray
Sakura
Pascarelli,
ESRF Magnetic Circular Dichroism
email: sakura@esrf.fr
Sakura Pascarelli

sakura@esrf.fr
Abstract
This lecture will give a general introduction to X-ray Magnetic Circular Dichroism. It aims a
large audience, with diverse academic background. An overview of polarization dependent X-ray
spectroscopies will be given, followed by an introduction to the dipole operator and dipole corevalence transitions. To conclude, the two step model and the sum rules will be explained in a
simple way.
Keywords
X-ray Magnetic Circular Dichroism, XMCD, polarization dependent spectroscopies

Polarization dependent X-ray spectroscopies
The figure below illustrates different kinds of polarization dependent X-ray spectroscopies:
Figure 1.
X-ray linear dichroism (XLD) employs linearly polarized X-rays. It probes the dependence of
absorption on the relative orientation between x-ray polarization and the crystallographic axis.
171
The electric field is used as a search-light that spots the number of valence holes in different
directions.
If the structure is anisotropic, then the number of valence holes is likely to be different in
different crystallographic directions. We can then define absorption coefficients
//
and
for
the two polarization directions parallel and perpendicular to a chosen crystallographic direction:
Figure 2.
The XLD signal is defined as:
XLD =
//
// +
Photon energy (eV)

Figure 3.
The polarisation dependence gives the symmetry of the empty orbitals. The figure above
illustrates the strong XLD observed at the Cu L2,3 edges (sensitive to the empty 3d levels) in the
cuprate layered compound LaSrCuO.
X-ray magnetic linear dichroism (XMLD) also employs linearly polarized X-rays. It probes the
dependence of absorption on the relative orientation between X-ray polarization and spin
direction. The electric field is used as a search-light that spots the number of valence holes in
different magnetization directions.
We define absorption coefficients
//
and
for the two polarization directions parallel and
perpendicular to the magnetization direction:
Figure 4.
172
The XMLD signal is defined as:
XMLD =
//
// +
If there is no magnetic (spin) order, i.e. we cannot define a magnetization direction, then the
XMLD signal is equivalent to the XLD signal: it probes the charge order in systems where the
absorbing atom has lower than cubic symmetry.
Figure 5.
In the presence of magnetic (spin) order, then spin-orbit coupling leads to preferential charge
order relative to the spin direction even in cubic systems, giving rise to an XMLD signal. The
XMLD signal at the absorption edge can therefore provide information on spin axis direction in
(anti)ferromagnetic systems. An XMLD signal can also be detected in the EXAFS region, and
provides information on local atomic displacements around the absorber atom induced by
magnetoelastic coupling effects (i.e. magnetostriction).
X-ray magnetic circular dichroism (XMCD) employs circularly polarized X-rays. It probes the
difference in absorption of left and right circularly polarized x-rays by a magnetic material. The
use of circularly polarized photons makes the absorption process spin dependent, because the
absorbed photon carries an angular momentum that it can transfer to the photoelectron.
We define absorption coefficients
and
R for the two polarization directions (circular left
and right) respectively. The XMCD signal is defined as:
L R
XMCD = L
+ R
We will see in the following that the XMCD signal provides information on spin and orbital
moment in magnetic materials. The figure below illustrates the different absorption for
circularly polarized X-rays at the Fe L2,3 edges, in pure Fe. The two spectra are obtained when
the photon angular momentum is parallel (antiparallel) to the sample magnetization axis. The
XMCD signal is shown on the panel to the right.
Figure 6.
173
The dipole operator and core-valence transitions: a refresher

The expression of the absorption coefficient in the dipole approximation can be written as:
where
is the dipole operator, with components:
Pq = q (xex + ye y + ze z )
with : = x, y , z the X-ray propagation direction and q = +1, 0, -1 the X-ray polarization states
(q photon angular momentum). For q=0, we have linearly polarized photons:
x0 = x = ex
y0 =
y=
ey
z0 =
z=
ez
For q = 1, we have circularly polarized photons. For circular polarization with k // z the
photons propagate along z, while the electric field vector rotates along a helix in the x, y plane, as
shown in the figure below :
=
z
1
( x i y )
2
Transitions induced by the dipole operator between electronic core and valence states can be
visualized in different ways ( atomic model, ligand field, band model) depending on the system
under study. The figure below illustrates this schematically for 2p core to 3d valence transitions.
Atomic Model
Ligand Field
Band Model
Figure 7.
Given the initial state (the excited core electron), the dipole allowed final states are those that
verify the selection rules. It is important to underline that the sum over all basis states of a shell
with angular momentum l is spherically symmetric.
174
The Hole Sum Rule

Sum rules link measured intensities with valence band properties. We will see in this section
how measured intensities can provide information on valence band properties. Atomic
quantities such as i) the number of empty states or holes Nh per atom, ii) the spin magnetic
moment ms per atom, or iii) the orbital magnetic moment mo per atom, are defined by
integration over the atomic volume, and are therefore isotropic quantities. To take advantage of
sum rules, it is important to make sure that the measured intensities are angular averaged. For
non-magnetic polycrystalline samples, measurements can be made with any X-ray polarization.
For non-magnetic single crystals, it is important to properly average over all sample orientations.
For magnetic polycrystalline or single crystals as above, but eliminating magnetic effects by
saturating the sample with a magnetic field parallel and anti-parallel to k and summing over the
two intensities.
The hole sum rule for the L2 and L3 edges in the 3d metals states that intensity of the combined
L2 and L3 white lines is directly proportional to the total number of d states above the Fermi
level, i.e. the number of holes Nh in the d band:
I L3 + I L 2 = C N h
This sum rule can be visualized in the figure below, that illustrates the L2 and L3 absorption
edges in the 3d metals Fe, Co, Ni and Cu. The intensity of the white lines decreases from Fe to
Cu, proportionally to the decrease of the number of 3d holes.
Figure 8.
The important intensity sum rule for the number of holes suggests that if we could make the
absorption process spin-dependent, then we could measure an intensity difference that
corresponds to the difference between the number of spin-up and spin-down holes, i.e. the
magnetic moment. This can be done using circularly polarized photons and is the origin of the
XMCD effect.
175
Conservation of angular momentum

We can make the absorption process spin-dependent by using circularly polarized photons,
because these can transfer their angular momentum to the electron spin. Lets see how this
happens.
Lets consider an atom in an initial pure quantum state:
J = total angular momentum

M = projection of J along the preferred magnetic axis defined by the unit vector m
And now lets consider a photon with angular momentum q in the direction of propagation:
Once the photon is absorbed by the atom, using the rules of vector addition, the total angular
momentum of the atom changes:
So, the total change in the projection of the angular momentum M is:
M = M ' M = q ( z m ) = 1
, if
z // m
The change in angular momentum is 1 depending on whether the photon helicity is parallel or
anti-parallel to the sample magnetization axis.
M =
1
(remember the selection rule on
M , the propagation direction of the photon has to be

z // m (remember this for later).
To achieve the highest possible change

parallel to the magnetization axis :
To conclude: the photon transfers it angular momentum to the photoelectron. If the initial state
has a non-zero angular momentum (i.e. 2p electron), then the photon can transfer its angular
momentum to the electron spin through spin-orbit coupling. The excited photoelectron is
therefore spin-polarized.
The Two Step Model for L-edge XMCD
We can explain the origin of the XMCD intensity at the L-edges using a two step model.
Step 1: A circularly polarized photon excites a photoelectron from a core level. It transfers its
helicity (angular momentum) to the photoelectron. If the photoelectron is excited from a spinorbit split level, the helicity of the photon can be transferred to the spin, through the spin-orbit
coupling.
176
The excited photoelectrons are spin-polarized. The amount of spin-polarization is proportional

to degree of circular polarization. For example, at the Fe L2 edge (2p1/2 3d):
[ Spin polarization is opposite at L2 and L3 edges because of the opposite spin orbit coupling l+s,
l-s]
Step 2: The exchange split valence shell with unequal spin up and spin down populations acts as
a spin detector. The photoelectron is captured into an unoccupied valence state: the transition
rate depends on the number of available final states with spin // the photoelectron spin. This is
proportional to the sample magnetization.
Figure 9.
In the figure above, the exchange split spin-down band is full: detection of spin-down electrons
is not possible (no available states).
Therefore, only spin-up electrons can be excited, and this leads to an important difference in
absorption probability between circularly polarized right and left photons, as schematically
illustrated in the figure below:
177
Figure 10.
The figure below illustrates in a qualitative way the origin of XMCD at the Fe L3 edge: the white
line is much larger when helicity is parallel to sample magnetization than when it is antiparallel.
Figure 11.
The Spin and Orbital Moment Sum Rules
We saw above that a sum rule could be derived which directly links the measured averaged X-ray
absorption intensity of a corevalence transition to the number of empty valence states Nh
(number of holes) per atom where C is a proportionality constant. Two other sum rules have
been derived which link measured spectra to the spin and orbital moment.
1. The spin sum rule links the XMCD intensities to the size of the spin moment per atom.
2. The orbital moment sum rule links the XMCD intensities to the size of the average orbital
moment per atom.

The figure below summarizes the three sum rules and provides the expressions linking the
measured quantities (A: integral of L3 XMCD signal; B: integral of L2 XMCD signal) to the
number of holes in the 3d valence band (Nh), the spin moment (ms), and to the orbital moment
(mo).
178
Figure 12.
K-shell XMCD
In the case of K-shell XMCD, the 1s core shell has zero angular momentum. Therefore there is
no spin-orbit coupling, and the photon cannot transfer its angular momentum to the
photoelectron spin (no spin polarized photoelectron). In this case, the photon angular
momentum is transferred to the photoelectron angular momentum. Dichroism at the K-edge
can be observed only if the valence shell possesses an orbital magnetic moment. This means that
the valence band empty density of states must have an imbalance of states with quantum
numbers +ml and -ml
Main properties of XMCD
Element selectivity
i.e. iron, copper, platinum (induced magnetism)
Orbital selectivity
Different edges of a same element different valence electrons
K edge (1s 4p)
Fe:
L2,3 edges (2p 3d)
Sum rules
Can separate orbital and spin contributions to the magnetic moments from the
integrated XMCD signal
Sensitivity << 1ML
Impurities, very thin layers, adatoms on surfaces
High penetration depth
Magnetism at extreme pressure (hard X-rays)
Presence of net <M> along k
Ferromagnetic, ferrimagnetic and paramagnetic systems
Angular dependence
Information on orbital moment anisotropy, magnetic anisotropy
Can be used for element specific magnetic imaging
References
Magnetism: From Fundamentals to Nanoscale Dynamics, Joachim Sthr, and Hans Christoph Siegmann.
Springer Series in Solid-State Sciences (2006).
179
Biological systems and high-pressure SAXS
Biological
systemsUK
and high-pressure SAXS
Nick Brooks, Imperial
College London,
email: n.brooks@imperial.ac.uk
Nick Brooks
Dept of Chemistry, Imperial College London, London, UK

nicholas.brooks@imperial.ac.uk
www.imperial.ac.uk/people/n.brooks
Abstract
Hydrostatic pressure has dramatic effects on the structure and stability of biological molecules
and their assemblies, and is a key thermodynamic parameter in the context of the biology of
deep sea organisms. Furthermore, high-pressure and pressure-jump studies are extremely useful
tools in biophysics and biotechnology, where they can be used to study the mechanism and
kinetics of lipid phase transitions, biomolecular transformations, and protein folding/unfolding.
This lecture will give an overview of the effect of pressure on the structure and assembly of
biomolecules (focusing on biomembranes) and the technology currently available for small angle
X-ray scattering studies of soft matter systems under pressure.
Keywords
Biomolecules, membranes, SAXS
Introduction
Over 70% of the earth is covered with water with an average depth of 3.8 km which exerts a
pressure of almost 40 MPa (400 bar). Despite such high pressures, life thrives in the ocean and
indeed over the past 30 years, pressure adapted organisms have been discovered in increasingly
extreme ocean conditions. The bottom of the Mariana Trench reaches 11 km below sea level,
exerting a pressure greater than 100 MPa (1 kbar)1 and even at these pressures, adapted bacteria
have been found. These organisms must have mechanisms to adapt their lipid membranes to
maintain their fundamental structure and mechanical properties.2 While high pressure
adaptation is a well-established phenomenon,3, 4 the regulatory mechanisms employed are poorly
understood and are the subject of great interest.
In addition to its direct relevance to the biology of deep sea organisms, high pressure can play a
key role in studying the structure and dynamics of biological assemblies. Hydrostatic pressure
can be used to drive structural changes in biomolecules and offers significant advantages over
other structure change triggers such as temperature and composition changes both at
equilibrium and during rapid changes: High pressure does not tend to disrupt intramolecular
bonding below 2 GPa, pressure can be applied and released from a sample extremely rapidly with
both increasing and decreasing pressure, and due to the rapid propagation of pressure, it
equilibrates throughout a sample quickly. Many structural changes in membrane assemblies take
place on the millisecond to second timescale and so by using fast pressure jumps, the
180
thermodynamic trigger variable can be decoupled from the structural change, allowing the real
time kinetics and evolution of these changes to be studied using fast probe techniques.
Fast pressure jumps unlock the potential of probing the kinetics of biomolecular structural
changes in real time, but to realise this, it is essential to couple high pressure technology to a fast
structure probe technique. Synchrotron small and wide angle X-ray diffraction (SAXS / WAXS)
is an ideal structural probe for these types of system and with recent developments in high flux
X-ray sources and fast detectors, the time resolution of these instruments ideally complements
dynamic structural studies of lipid membranes.
Biological systems under high pressure
Increasing pressure will always drive a system towards smaller volume. Many biological
molecules and biomolecular assemblies are stabilized through non-covalent interactions, so
pressures up to a few hundred MPa (Fig 1) can cause significant changes to their structure, and
consequently their function. Two of the most important biological structures are lipids
membranes and proteins and the structure of both of these is dependent of pressure.
Figure 1. The pressures required to cause structural changes in many biomolecular systems is in the hundreds of MPa
range. For comparison, the pressure in the deepest ocean trench is just over 100 MPa.
Lipid membranes
Lipid membranes are amongst the most important of all biological structures. In addition to
maintaining basic cell integrity and compartmentalisation, lipids are known to play a vital role in
cell signalling, and there is increasing evidence that the micro-mechanics of membranes help to
modulate the activity of proteins, peptides, channels and receptors embedded within them.5
Lipid molecules consist of a hydrophilic head group and one or more hydrophobic hydrocarbon
chains, increasing hydrostatic pressure results in a reduction in the conformational freedom of
the lipid hydrocarbon chains, however, the headgroup region is effected significantly less. The
overall result is a reduction the cross sectional area of the lipid tail region and an extension of the
181
hydrocarbon chains (Fig 2). It is important to note that the effect of increasing pressure is
qualitatively similar to decreasing temperature.
Figure 2. Hydrostatic pressure tends to cause a reduction in the conformational freedom of lipid hydrocarbon chains.
This leads to the chains having a reduced cross sectional area but increased extension.
While the pressure dependent structural change in a single lipid molecule may seem relatively
small, these effects can have significant implications for the structure of lipid assemblies. The
reduction in chain cross sectional area changes the preferred interfacial curvature of the lipid
molecules and when this effect is large enough, it may induce a phase change for example a lipid
that self assembles into an inverse hexagonal structure6 under suitable conditions may adopt a
flat bilayer structure when the pressure is increased (Fig 3). Pressures up to approximately 400
MPa tend to be used for these types of investigation.
Figure 3. Pressure induced changes in the lipid molecular packing shape can cause large scale phase changes in lipid
assemblies.
In addition to causing changes in the curvature of lipid membranes, increasing pressure may also
cause bilayers to change from the fluid structure that is ubiquitous in living cells where there is
182
rapid diffusion within the bilayer, to a gel structure, where the lipid molecules are close packed
within the bilayer and the hydrocarbon chains are effectively in a fully extended conformation.
Importantly, this gel structure cannot provide the required functions for a living cell membrane
and so it is thought that deep sea organisms must modulate their membrane composition to
maintain fluidity amongst a range of other factors.
More subtle changes in pressure can also have an important effect on the lateral structure of
lipid membranes. For example, model lipid membranes formed from a high melting point (Tm)
lipid, low Tm lipid and cholesterol (Chol) can exhibit coexistence between two different fluid
phases (Fig. 4); liquid disordered domains (Ld) where the lipid hydrocarbon chains are molten
and liquid ordered (Lo) domains7 where the lipids exhibit fast diffusion within the bilayer but the
hydrocarbon chains show a high degree of conformational ordering. This lateral phase
separation can be induced either at low temperature or high pressure. Pressures changes of as
little as 5 MPa can be used to induce these lateral structural changes and generally pressures of
less than 100 MPa have been used to investigate these systems. Similar microdomain structures
that form on short length- and time-scales are thought to play a key role in cellular functions
such as signal transduction and the sorting and transport of lipids and membrane proteins.
Figure 4. Pressure can induce lateral phase separation in mixed lipid membranes formed from a high melting point lipid
(green) a low melting point lipid (blue) and cholesterol (grey rods).
In addition, pressure can affect the micromechanical behaviour8 and viscosity9 of lipid
membranes.
Proteins
Proteins are responsible for an enormous range of biological processes and functions and they
are structured on a number of levels. Many of these types of structuring can be perturbed by
changing pressure and importantly, using pressure changes to drive folding or unfolding of
proteins can underpin The primary structure of a protein describes the amino acid sequence of
the polypeptide chain that makes up the protein, this is a covalently bonded structure and so is
generally considered not to be sensitive to the pressures discussed here. The secondary structure
refers to structuring of the polypeptide chain such as -helix or -sheet formation, pressures of
up to 2 GPa have been used to investigate secondary structure perturbation. Tertiary structure
or the 3 dimensional protein fold can be perturbed by pressures of several hundred MPa or more
and the quaternary structure or assembly of protein subunits can be disrupted by similar
pressures. Usually, proteins tend to denature (or unfold) under pressure (Fig. 5) and it is
generally thought that this is due to void volumes within the native protein structure. The total
183
volume of a protein and its solvent can be reduced if the protein unfolds because the solvent can
then access empty space that was previously within the folded protein structure.
Figure 5. Increasing pressure tends to cause unfolding of proteins. Different types of protein structuring can unfold at
different pressure.
The kinetics of pressure induced protein unfolding (or any other structural transition where the
rate varies with pressure) can be interpreted using a volume of activation model:
(1)
Where Va is the volume of activation, k(p) and k0 are the rate constants at relative pressure p
and atmospheric pressure respectively, R is the gas constant and T is the temperature. The
volume of activation can be interpreted using transition-state theory as the difference in volume
between the transition state and the volume of the reactants at the same pressure. This can be
thought of as an elastic barrier to transformation, in much the same way as the activation energy
for a reaction is thought of as a thermal energetic barrier to a reaction.
High pressure small angle X-ray scattering (SAXS)
Biomelecular assemblies tend to have characteristic length scales on the nm or even m scale
meaning that scattering tends to takes place below 1. Moreover, biomolecules are
predominantly composed of light atoms meaning that only approximately 1 in 104 incident X-ray
photons are scattered. This presents some significant challenges for X-ray diffraction or
scattering experiments. Exploiting the time resolution available with pressure jump technology
to investigate structural change mechanisms and kinetics requires a high intensity X-ray source
and so high pressure SAXS experiments are almost always carried out at synchrotron X-ray
sources.
One of the challenges of carrying out high pressure SAXS experiments is designing a robust
sample cell that can simultaneously withstand the required pressures while allowing X-rays into
and out of the cell and maximising the diffraction angle that can be observed.
184
A range of high pressure small angle X-ray sample cells have been produced that are tailored for
experiments on soft matter and biomolecular systems. These allow fine control of pressure and
temperature and in many case allow fast pressure jumps to be performed. These allow
experiments to be carried out at up to 1 GPa.10-17 In addition, there has been a significant amount
of X-ray scattering work carried out on proteins using diamond anvil cells, however these are
extensively described elsewhere and so will not be discussed in detail here.
The robust and versatile system designed by Woenckhaus et al.14 is particularly noteworthy as it
represents a benchmark for more recent SAXS pressure cell development16, 17 (Fig. 6) and it has
facilitated a wide range of exciting high pressure and dynamic experiments on lipid systems.18-26
This system can perform both static high pressure and pressure jump experiments between
atmospheric pressure and 0.7 GPa (7 kbar) at temperatures from -40 to 100 C. This cell employs
0.8 mm thick diamond as X-ray windows which offers a transmission of over 80% for 17 keV Xrays.
Figure 6. Drawing of the high pressure SAXS cell available at beamline I22, Diamond Light Source.17, 27
A number of soft matter X-ray pressure systems have been developed or used extensively at
major synchrotron SAXS beamlines including beamline ID2 at the European Synchrotron
Radiation Facility,14, 18, 28 beamline A2 at the Deutsche Synchrotron,22 the Austrian SAXS
beamline at Elettra,12 BL9 at DELTA,16, 29 station G1 at the Cornell High Energy Synchrotron
Source,15 beamline 18ID at the Advanced Photon Source, Argonne and beamline I22 at Diamond
Light Source.17
In the case of membrane assemblies, high pressure and pressure jump SAXS can offer a unique
insight into the energetics and kinetics associated with the structural reorganisations described
above. Concentrated lipid assemblies can exhibit extended ordering (for example in a liquid
185
crystalline lamellar phase) and so show a series of Bragg peaks in their diffraction pattern which
can be indexed to find the lattice parameters associated with the self-assembled structure.25, 30
In contrast, SAXS patterns from protein solutions tends to show a continuous scattering profile.
This is usually analysed to find the proteins radius of gyration, from which the extent of folding
can be inferred.31 However, recent exciting developments in SAXS pattern modelling and
refinement now offer the possibility of obtaining low resolution protein structures from SAXS
data.32
Pressure jump experiments can very rapidly produce an enormous amount of diffraction data
and there is currently a drive to develop improved tools for automated SAXS analysis in a
number of areas. As mentioned above, lipid assemblies generally used for pressure jump
experiments show sharp diffraction peaks and batch analysis software28 allows sequences of two
dimensional diffraction images to be integrated to give one dimensional patterns and the peaks
diffraction peaks to be fitted providing phase identification, lattice parameters and intensity data.
Complementary techniques
High pressure NMR
High pressure NMR can provide information on the dynamics of both membranes and
proteins.33 Several high pressure NMR systems have been developed,34 however the high pressure
NMR probe developed by Bonev and Morrow35 was designed specifically for use with soft
materials and has been used extensively to study model membrane samples36, 37.
High pressure optical microscopy
There have been exciting recent developments in design and use of high pressure optical
microscopy systems, allowing bright field,8, 38, 39 polarizing.40 fluorescence,41-44 and single molecule
45
microscopy, at pressures as high as 700 MPa 42. High pressure microscopy is extremely
complementary to high pressure SAXS, while it does not offer the molecular resolution of X-ray
experiments, it can offer 2D or 3D localisation of membrane components or proteins (Fig. 7). In
addition, it can provide relatively simple access to high time resolution and can be performed inhouse rather than being restricted to large-scale central facilities.
Figure 7. Pressure induced phase separation in lipid bilayer vesicles. (a) shows the induction of many small nucleated Lo
domains and subsequent increases in pressure do not cause domain coalescence. (b) shows an alternative domain growth
mechanism, where an increase in pressure leads to the merging and growth of Lo domains. Scale bars are 30 m.44
186
Conclusions
High hydrostatic pressure is an extremely powerful tool which can be used to study and
manipulate biomolecular structures and dynamics. With recent advances in high pressure
technology and probe facilities, this tool is now available to a wide user base. There is a great deal
to learn about biomolecules and life under pressure and this new technology is likely to facilitate
many further exciting studies in the future.
Acknowledgments
We would like to thank Diamond Light Source and the European Synchrotron Radiation Facility
for long standing collaboration and provision of synchrotron beamtime. The development of this
work was supported by UK EPSRC Programme grant EP/J017566/1.
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188
High-pressure crystallography of pharmaceutical drug molecules
High-pressure
crystallography
of pharmaceutical
drug molecules
Francesca
P. A. Fabbiani,
Georg-August-Universitt
Gttingen,
GZG, Abteilung
Kristallographie, Goldschmidtstr. 1, D37077 Gttingen, Germany
Francesca
P.A. Fabbiani
email:
ffabbia@gwdg.de
Dept Crystallography, Univ. Gttingen, Gttingen, Germany
homepage:
http://hiprcryst.uni-goettingen.de
ffabbia@gwdg.de
www. hiprcryst.uni-goettingen.de
Abstract
Why should we study pharmaceutical drug products under pressure, in particular by

crystallographic techniques? A concise answer to the question may be: to understand the
mechanical properties and explore the crystallisation and phase diagrams of drug products more
thoroughly. After a brief and general introduction into the topics of polymorphism and drug
manufacturing, a range of possible applications of high-pressure research will be presented
through selected case studies of pharmaceutically-relevant compounds.
Keywords
Pharmaceuticals, polymorphism, crystallisation, in situ techniques
Introduction
The physicochemical properties of a material are, to a good approximation and ignoring size
effects, largely dependent on the 3D arrangement of the component atoms and/or molecules in
the solid state. Elucidating this 3D-arrangement, which for crystalline materials is termed crystal
structure, is the research goal of scientist in industry and academia working in fields as diverse as
materials engineering, drug development and structural biology. In the particular case of a drug
molecule or active pharmaceutical ingredient (API), different properties such as solubility,
hygroscopicity, density, stability and hardness can be understood, controlled and optimised by
knowledge of different crystal structures. 1, 2 This knowledge also forms the basis of patent
protection for pharmaceutical companies. The understanding of a material at the structural level
can give an insight into its properties and function, as attested by the numerous research efforts
in the area of structure-based drug design and structure determination of biomolecules.
High pressure is a formidable tool for probing structure, bonding and reactivity: there are several
more degrees of magnitude that can be readily probed by pressure than those available by
temperature alone. By probing the relevant pressure-temperature space, systematic highpressure studies can be a useful tool for studying materials properties, without the immediate
need of modifying either chemical structure or synthesis/crystallisation conditions, provided the
appropriate experimental and data analysis tools are used. Throughout the School, examples
spanning a wide range of materials will be given. These lecture notes focuses on the application
of high-pressure crystallographic and crystallisation techniques on APIs and pharmaceuticallyrelevant compounds.
189
Physical forms in the pharmaceutical industry

Just as any other material, drug molecules are capable of forming a variety of physical forms. In
these notes, the term physical form defines any form in which a molecule can exist in the solid
state. This definition encompasses both crystalline and amorphous material. 3 For singlecomponent crystals that differ in their crystal structures, the physical forms are termed
polymorphs. When distinct chemical species crystallise together, a multicomponent crystal is
formed. Hydrate, solvates, salts, co-crystals and inclusion complexes are all examples of
multicomponent crystals; these can also be polymorphic, provided the chemical composition is
invariant.
In pharmaceutical-related literature, the term physical form is often associated with further
buzzwords, e.g. physical form screening, physical form characterisation, physical form
discovery, physical form selection. As the terms suggest, these refer to processes encountered
during different stages of the lifecycle of a drug while still on the industrial premises, primarily
during the processes of late-stage drug discovery and throughout drug development with most
activity actually taking place at the discovery-development interface (Fig. 1). 4, 5 The road of an
API from a medicinal chemistry laboratory to a pharmacys shelf is a long and winding one. On
average, it takes 8-12 years for this process to reach full maturity. Hence, for instance, a number
of physical forms of an API may be discovered during a crystallisation screen; after
characterisation of physicochemical properties (e.g. solubility) a particular physical form may be
selected for preformulation (early development), e.g. on the basis of the availability of a feasible,
large-scale crystallisation process. Different pharmaceutical companies apply different strategies
and policies to physical form discovery (only the clinical phase of drug development is more
standardised to comply with regulatory agencies), but in 2004, Gardner et al. convincingly
advocated for a more thorough investigation of physical forms early in the discovery process, e.g.
by means of high-throughput screening. 6 Nowadays, solid-state screening is typically performed
in house or contracted out to specialised companies (see for instance Solvias, Polycrystalline,
Crystallics and Aptuit to name but a few). Despite some variations in the order of the actions in
the pipeline, there is a general consensus that a screen should be as comprehensive as possible,
i.e. no forms should be overlooked. This is because very few systems are genuinely monomorphic
or do not crystallise as solvates. Formation of co-crystals adds another dimension to the screen;
pharmaceutical co-crystals (recently reviewed 7 ) are currently attracting particular attention as
they have the potential to fundamentally alter an APIs solid-state properties, or even provide
dual-drug products by combing different APIs. A word of caution here: with the Food and Drug
Administration (FDA) in the US classifying co-crystals as drug-product intermediates, i.e. not a
new API, and the European Medicines Agency (EMA) in Europe suggesting to consider cocrystals as APIs, the regulatory aspects of drug co-crystals are still not fully settled, and the
pharmaceutical industry is hence proceeding with caution in this field.
190
Figure 1. Schematic flow diagram of stages of drug discovery, development and approval, with a focus on solid-state
drug characterisation.
Why study pharmaceuticals at high pressure?

Given the above preamble: how does high-pressure fit into the equation and why should one
study pharmaceutical drug products under pressure, in particular by crystallographic
techniques? As a scientist working in academia, the question as to why this may be interesting is
not difficult to answer. Besides the thrilling experience of growing single crystals in a DAC in a
matter of minutes under a microscope and unravelling new crystal structures by diffraction in a
matter of few hours, high-pressure techniques enable the exploration of another portion of a
materials phase or crystallisation diagram. Hence, when combined with ambient-pressure and
variable-temperature studies, they enable a more rigorous approach to the study of
intermolecular interactions and phase transitions. Such an exploration can be useful on a
number of practical fronts, for instance: a) to ensure no stable forms have been missed in
ambient-pressure screening experiments; b) to help identifying all possible forms of an API,
thereby expanding patent protection; c) to better characterise forms that are metastable at
ambient pressure but are stable at high pressure, and can be subsequently recovered at ambient
pressure, d) to monitor in situ possible phase changes that may occur during drug processing
and manufacturing, e.g. phase transition during tableting or amorphisation during milling.
The remainder of these notes will provide a brief overview of applications of high-pressure
research in the pharmaceutical industry, covering some aspects in greater detail through selected
case studies.
Pressure in the pharmaceutical industry: manufacturing processes
In the pharmaceutical industry mechanical action on APIs in solid form is used in a variety of
manufacturing processes that combine compression and shear treatment; the former is also
191
known as impact treatment when the rate of compression is very fast. The topic of
mechanochemistry and its relevance to pharmacy has been covered in great detail in a number of
publications. 8, 9 , 10 , 11 , 12 , 13 In response to an applied load (force, e.g. through mechanical action), a
material will be subject to stress (which, depending on the loading conditions, may or may not be
uniformly distributed). The stress will in turn generate strain (deformation) in the material. It is
well known that mechanical action can induce phase transitions (or even chemical reactions) in
APIs; however, with the exception of work carried out in academia, the mechanisms behind
these transformations are usually either not investigated or are poorly understood.
Milling/grinding and tableting are two processing techniques commonly used in the
pharmaceutical industry.10, 14 Milling and grinding machines operate on the principle of using
mechanical action to reduce particle size, reduce particle size distribution or simply de-lump
powders. Milling of an API can play an important role for the bioavailability of the API, e.g. by
obtaining pre-determined particle size. Bioavailability is normally defined as the fraction of and
rate at which an API reaches the site of action (usually by being absorbed into the blood stream)
with respect to the administered dose. Tableting also makes use of mechanical action to bind
API and excipients together in a tablet; the reader should note that in the context of dosage
forms, tablets are the most common way of formulating an API. Before the actual tableting step,
an API needs to be mixed with excipients, e.g. to reach the desired dissolution rate. Direct
compression of API and excipients is rare; a formulation containing a mixture of API and
excipient is usually obtained by granulation and not by simple mixing of API and excipient.
The scope of granulation is to obtain particles of same size; this is an important step as it
ensures, for instance, that once made, all tablets have the same weight. During the granulation
process, which can be carried out on dry or wet material, particles are compacted to increase the
grain size, thereby facilitating the tableting step, e.g. by changing the materials flow properties.
Because granulation usually results in a lump of material, known as slug, low-shear milling is
subsequently applied to break up the lumps and obtain a standardised particle size distribution
prior to actual tableting.
Even if pharmaceutical processes result in non-hydrostatic stress states, hydrostatic (or quasi
hydrostatic) diffraction experiments in the diamond anvil cell (DAC) provide a more controlled
environment and allow to investigate in situ processes such as phase transitions and
crystallisation, providing insight at the atomic level in the form of crystal structures. In practice,
experiments make use of in situ high-pressure crystallisation and/or direct compression
techniques. In situ high-pressure crystallisation techniques offer the advantage that new
crystalline phases, if they exist, can be usually obtained at lower pressures than they would be by
direct compression (c.f. kinetic barrier to molecular rearrangement in the solid state vs. working
from solution)obviously, when looking for high-pressure solvates or hydrates crystallisation
from solution is also the preferred technique. In terms of actual high-pressure diffraction
experiments, the majority of studies are performed on single-crystal specimens as these yield the
most accurate and precise structures. Thanks to the advent of Mo- and Ag-microfocussed
192
laboratory sources, the experiments can be conveniently performed in a home laboratory setting,
though there are sometimes great advantages associated with going to the synchrotron (e.g. large
number of samples to screen or availability of small crystals). Powder diffraction is a powerful
tool for rapidly screening the behaviour of a system as a function of pressure and for probing
the effects of compression rates and crystallite size (c.f. kinetic barrier and number of nucleation
points) to induce polymorphic transitions; however, it is generally less successful when applied
for the purpose of structure solution from data collected on in situ grown polycrystalline
samples (oriented material, large crystallites).
High-pressure techniques for characterisation of APIs: Case studies
Four case studies, in which high-pressure crystallographic techniques feature prominently, are
investigated in more detail below. These exemplify the importance of using a multidisciplinary
approach in the study of polymorphism and solid-state properties of pharmaceutically-relevant
compounds.
Figure 2. Chemical structures of the compounds detailed in the case studies.
Case study 1: Dalcetrapib
This case study highlights the power of combining crystal structure prediction studies together
with rationally-planned crystallisation experiments to perform a thorough polymorph screen, in
which the predicted lowest-energy structures are found experimentally and the identity of the
thermodynamically most stable form at ambient-pressure and temperature conditions is
confirmed.
Dalcetrapib, a cholesterol ester transferase protein inhibitor intended for the prevention of
atherosclerosis, was in development at Hoffmann-La Roche until 2012. Recent studies have
demonstrated it could find potential use in treatment of cardiovascular diseases for a genetic
subgroup 15 and sparked renewed interest in this compound. To date, with its ten rotatable
bonds, the compound is the most complex API for which both crystal structure prediction (CSP)
193
and high-pressure experiments have been performed and published. 16 At ambient-pressure

conditions, Dalcetrapib exists in two polymorphic forms: form A, which is structurally
disordered, stable at ambient temperature and is reproducibly formed by solution crystallisation,
and form B, which is structurally ordered and can be obtained by cooling form A below 186 K.
From the point of view of drug development, the existence of this low-temperature form is not
problematic since very low temperatures are needed to induce the transition, which is fully
reversible (the two forms are enantiotropically related). A state-of-the-art crystal structure
prediction study (CSP), located both forms at the bottom of the lattice energy landscape and
correctly described the structural disorder. Interestingly, the CSP study also indicated the
presence of two further structures, within a window of less than 1 kJ mol-1, which could
correspond to a more dense and thermodynamically more stable polymorph. Pressuredependent lattice energy calculations indicated that at high pressure these structures would be
significantly more stable, with the crossover point occurring at ca. 0.15 GPa and the energy gap
increasing to ca. 5 kJ mol-1 at 1 GPa. Hence, CSP provided a clear crystallisation recipe for a new
form. This recipe was implemented and form C was crystallised in the 0.02-0.50 GPa pressure
range from aqueous solution. The structure of a crystal grown in situ from solution was solved
by single-crystal X-ray diffraction, not only confirming the identity of the structure found by
CSP but also providing an experimentally-determined disordered model, which could be used to
further fine tune the CSP results in terms of energy ranking of the predicted structures. To
round up the study, a series of recovery experiments were undertaken. Given that samples
crystallised from solution at high pressure immediately convert to form A when pressure is
released, recovery trials were performed on form C crystallised in situ at high pressure from the
melt. This was feasible because the melting point of the compound is rather modest (ca. 338 K).
Form C could be recovered at ambient pressure and it was found to convert to form A on a
timescale of hours, providing definite proof that form A is indeed the most stable form at
ambient-pressure and ambient-temperature conditions; this is an important finding, as it
demonstrates that form C would not pose problems in late-stage development of Dalcetrapib. As
the case of Ritonavir shows, marketing an unknowingly metastable form can have disastrous
consequences in drug manufacturing. A subsequent publication notes that the existence of
Dalcetrapib form C at such modest high pressures and the structural disorder in both forms A
and C may have implications for the mechanical behaviour of crystals of the most stable form if
subjected to pressure during processing. 17
Case study 2: Chlorpropamide
This case study gives an example of a highly polymorphic API for which high-pressure forms have
been identified by the use of complementary diffraction and spectroscopic techniques and for
which the complex high-pressure polymorphic behaviour cannot be fully probed on the basis of
hydrostatic compression experiments alone.
194
Chlorpropamide is a sulfa drug used in the treatment of Type 2 diabetes. Its solid-state
polymorphism has been the subject of several investigations and the comprehensive and
extensive studies from Boldyreva et al. feature prominently in the literature (the reader should
consult reference 18 as a starting point for further reading). The Cambridge Structural Database
(CSD) contains entries and full structural data for nine polymorphs. Five polymorphs exist at
ambient conditions, three are low-temperature polymorphs and one is a high-pressure
polymorph. Of these nine polymorphs, six were included in a thorough analysis by Cruz-Cabeza
and Bernstein, 19 who reported that the compound has the largest number of true conformational
polymorphs (five; N.B. a preliminary analysis seems to indicate that this number is unchanged
when all nine polymorphs are considered) reported in the CSD and indeed one of the highest
number of polymorphs overall. This has been ascribed to the fact that this molecule contains
rotatable-bonds, viz. a terminal propyl group and benzensulfonamide moiety, that are prone to
both conformational change and adjustment. As defined by Cruz-Cabeza and Bernstein: Any
change in a given single rotatable bond (henceforth R-bond) of a molecule always affords a new
conformation, but it affords a new conformer only if the conformational change goes through a
potential energy barrier into a different potential energy well. Conversely, conformational
adjustment is defined when adopting a new conformer is not associated with crossing an energy
barrier on the potential energy surface.
The commercially available form of chlorpropamide is termed -form and is also known as the
A-form. The high-pressure polymorph found in the CSD, , is formed by compression above 2.8
GPa of the -form in a saturated ethanolic solution, as confirmed by high-pressure single-crystal
and powder X-ray diffraction. The first-order phase transition is reversible and is accompanied
by lowering of the crystal symmetry and twinning. The high-pressure polymorphism of this
compound had been the subject of some debate in the literature. A partial transformation of the
-form to the -form (the high-temperature form of the compound, also known in the literature
as form C) by compression to 196 MPa at ambient temperature was first reported by Ueda et al.
during compaction experiments, 20 subsequently by Otsuka et al. 21 and more recently by
Wildfong et al. 22 Two phase transitions were reported by Raman spectroscopy when using
ethanol as pressure-transmitting medium (PTM). 23 In contrast, dry powder samples investigated
by synchrotron powder X-ray diffraction up to 5.5 GPa 24 did not provide clear evidence for such
distinct transitions (there was some indication of changes above 4 GPa but the quality of the
diffraction patterns and possible loss of hydrostaticity could not provide unambiguous evidence).
An investigation by solid-state NMR up to 800 MPa and in the 90-300 K temperature range did
not show any evidence of a transition. 25 In this respect, the transformation that occurs in
a saturated ethanol solution highlights the importance of kinetic factors in favouring or
hindering phase transitions. In a more recent investigation, samples of the -form have been
investigated by Kichnov et al. by Raman spectroscopy (up to 24.6 GPa) and by synchrotron
powder X-ray diffraction (up to 4.4. GPa) using no PTM. 26 The authors found two phase
transitions occurring at ca. 1.2 and 3.0 GPa. The first one leads to form AI, with monoclinic unit-
195
cell parameters distinctively different from any of the known phases (no further structural details
are given in the publication); the second one, form AII, shows some differences in the unit-cell
parameters with respect to AI, however no cell parameters or structure are given by the authors.
Amorphisation was reported to occur above 9.6 GPa. The authors conclude their papers by
stating that differences in the results of high-pressure investigations by different authors can be
explained by effect from inner stresses and strains due to quasihydrostatic conditions during the
experiments in comparison with previous ones. However, the presented result clearly indicates
that the stability of the initial form-A of chlorpropamide may be compromised during tableting or
grinding processes. On the basis of the evidence given in the literature it would seem fair to say
that the exact high-pressure behaviour of this material is still not fully understood and the
existence of further polymorphs in the 0.1 MPa-5 GPa pressure range cannot be ruled out.
Case study 3: Calcium fumarate trihydrate
This case study gives an example of how to derive structure-property relationships using a
combination of nanoindentation and hydrostatic compression studies. An understanding of the
elastic and plastic properties of a material at the structural level is highly relevant to the
pharmaceutical industry, particularly when considering that tableting is the most common
process of drug manufacturing.
Calcium fumarate is used as a food additive, as an acidity regulator, and can be found as E367 on
the packages of food sold in the European Union. Calcium fumarate trihydrate has been
classified as a dietary supplement by the FDA although instances of its use in food or beverages
are not widely reported. Formally, the crystal structure of the trihydrate corresponds to a 1D
coordination polymer. In a very elegant study, Sun et al. have studied the mechanical (elastic and
plastic) properties of the compound in its single-crystal form using nanoindentation and highpressure single-crystal X-ray diffraction, the latter performed by compressing the sample up to
1.36 GPa. 27 The diffraction data provided detailed structural models as a function of pressure, in
particular giving details on the anisotropy of structural distortions upon compression and
allowing the determination of the bulk modulus [20.3(4) GPa] for the compound, which was
found to be significantly higher than those found in small molecule pharmaceutical crystals
constructed via weak interactions, but much lower than the inorganic dietary supplements. The
bulk modulus can be related to the elastic recovery of a powder after having been compacted
during the tableting process, i.e. during decompression (springback) and after actual ejection
from the die. The elastic modulus, hardness, yield stress and creep behaviour of the compound
determined from the nanoindentation experiments performed on oriented samples again
highlight the anisotropic response of the material. The nanoindentation results were correlated
with a careful analysis of the crystal structure for the derivation of structure-property
relationships. Hence, for instance, the anisotropic elastic properties were rationalised in terms of
the spatial distribution and frequency of specific structural motifs along different
crystallographic directions; here the focus was on a) CaOCa linkers, which are relatively sti,
196
b) hydrogen bonds, which are comparably softer, as well as c) fumarate ligands and their
orientation with respect to the Ca-Ofumarate-Ca chains. The authors also notably provide a
plausible structural mechanism for plastic deformation of the compound, where slipping of the
Ca-Ofumartate-Ca chains is facilitated along the c-axis, that is the crystallographic axis along which
the hydrogen bonds have the largest component, in line with the observation that these are
inclined to exhibit more plasticity than coordination or covalent bonds. In general, the presence
of slip planes in a crystalline API allows for plastic deformation, which is a highly desirable
property for direct compression as it facilitates the process of compaction into a tablet.
Case study 4: Glycolide
This case study examines the polymorphism of a biocompatible and biodegradable material used
in medicine and the pharmaceutical industry, providing an example of large-scale high-pressure
synthesis, seeding crystallisation, lattice energy calculations and disappearing polymorphism.
Glycolide is the precursor to the polymer polyglycolic acid (also known as polyglycolide or PGA)
and one of the monomers of poly(lactic-co-glycolic) acid (PLGA). Both polymers are
biocompatible and biodegradable and have been approved by the FDA and EMA for the purpose
of parenteral and topical drug delivery systems and for biomedical applications (e.g. for surgical
sutures and grafts). For instance, PLGA-based nanoparticles are used for cancer therapy to
deliver anticancer drugs in encapsulated form.
Hutchison et al. have investigated the solid-state polymorphism of glycolide by means of singlecrystal and powder X-ray diffraction, large-volume high-pressure experiments, Raman
spectroscopy and PIXEL lattice energy calculations. 28 The authors obtained a previously
unknown polymorph at 0.6 GPa both in the DAC and in bulk, using a large-volume press, and
recovered the material at ambient-pressure conditions to successfully perform seeding
crystallisation experiments. The spectroscopic work not only provided further characterisation
of the novel polymorph but also served the purpose of confirming that no polymerisation
reaction occurred at ambient temperature up to a maximum pressure of 8.0 GPa. The work also
highlights the use of theoretical calculations, in this case PIXEL lattice and interaction energies
calculations, which confirmed that at ambient pressure, the high-pressure form, form II, is less
stable than the known form, form I, by approximately 25 kJ mol-1 despite the latter being
strikingly less dense (1.619 g cm-3 and 1.680 g cm-3 for forms I at 296 and II at 293 K,
respectively). The reader should note that the so-called density rule, one of the rules used to
predict the thermodynamic relationships between polymorphs, see references 1 and 2 for further
details, is arguably the least effective one and tends to works less well for H-bonded solids. This
rule, according to which a modification of lower density is less stable at absolute zero 29 has
many exceptions, paracetamol and Ritonavir are two well-known examples, and Hutchison et al.
correctly point out its limitation. One of the most notable results of the work by Hutchison et al.
is that it provided an example of using high-pressure techniques for the synthesis and
subsequent recovery of metastable forms at ambient-pressure conditions. This is a welcome
197
addition to other examples reported in the literature (see for instance references 30, 31, 32 and
33). The authors showed that form II transforms to form I over the course of time. Most
interestingly, after fist succeeding in obtaining form II and using it for seeding over the course of
several experiments, the authors, during reproducibility checks, consistently obtained crystals of
form I only, giving rise to speculations that their laboratory became contaminated with this form
and hence leading to another fascinating example of disappearing polymorphism. 34
Conclusions
In the pharmaceutical industry, the phenomenon of polymorphism and the existence of multiple
physical forms in general can be both a nuisance and an opportunity. There is no escaping the
fact that few molecular organic compounds are not polymorphic; McCrone famously stated that
every compound has different polymorphic forms and that, in general, the number of forms
known for each compound is proportional to the time and money spent in research on that
compound; 35 according to Khnert-Brandsttter: Probably every substance is potentially
polymorphic. The only question is whether it is possible to adjust the external conditions in such a
way that polymorphism can be realised or not. 36 Sucrose, naphthalene and ibuprofen are three
compounds commonly found in a chemical laboratory that were thought of defying these
widely-accepted statements. In 2008 a second crystalline form of ibuprofen was reported to
form from the supercooled liquid. 37 In 2012, sucrose was reported to undergo a phase transition
at 4.8 GPa. 38 While diffraction studies up to 13 GPa do not point to a phase transition, 39, 40 , 41 the
case of naphthalene is not yet settled: Bridgman 42 reported a sluggish phase transition at ca. 3
GPa on the basis of volumetric measurements, with some spectroscopic evidence for such a
transition reported in subsequent studies. 43,44 It becomes apparent that the quest of polymorphs
requires one to probe the experimental space that goes beyond what are commonly referred to
as ambient conditions, or as put by Bernstein: The caveat here is that the frame of reference is
that the vast majority of these crystallizations have been carried out under normal
conditionsatmospheric pressure and close to ambient temperature or up to the boiling points of

various solvents employed. 45 The high-pressure examples covered in these notes clearly lend
credibility and hard evidence in support of this statement. Perhaps one could argue that at
sufficiently high pressures any organic compound will either transform to a new polymorphic
form or will eventually become amorphous; obviously, in the context of pharmaceuticals, those
physical forms that can be obtained at the lowest end of the high-pressure scale, or are at least
recoverable, will be of most interest.
The case studies also illustrate the key role played by high-pressure crystallography and
emphasise the importance of using a combination of techniques for a better description and
understanding of APIs. In terms of techniques, only a handful has been mentioned in these
notes. They include solid-state diffraction (single-crystal and powder) and spectroscopic
techniques (IR, Raman, and NMR), computational methods (DFT calculations, ab initio
structure prediction, energy calculations based on semi-empirical methods) and
198
nanoindentation. Other techniques have not been mentioned but are nevertheless of interest and
relevance in the study of pharmaceuticals. Notable examples include: high-pressure total
scattering experiments for the study of disordered crystalline materials or amorphous materials
(although the majority of APIs are marketed in their crystalline forms, stable amorphous forms
can be a viable option); the recently revived volumetric compression studies, 46 as a rapid and
effective way to monitor possible phase changes on compression of solid and liquid phases,
provided the phase change involves a volume discontinuity; high-pressure calorimetry to provide
rigorous thermodynamic data with which pressure-temperature phase diagrams can be
constructed and precise phase relationships can be determined (see elegant paper on the latent
polymorphism of Rotigotine 47 and on polymorphism of piracetam 48 for an introduction to the
field).
These notes have focussed primarily on solid-state processes and even if the phenomena of highpressure crystallisation from solution and solution-mediated transitions have been discussed in
some details, only the outcomes of such experiments, in terms of physical forms end products,
have been given. A better understanding of the process of high-pressure crystallisation would be
desirable. High-pressure solubility and nucleation studies could shed some light in this direction.
In this context, a recent article reported an experimental and theoretical high-pressure aqueous
solubility study of paracetamol and piracetam, demonstrating that the decrease in solubility due
to (rapid) pressurization is often balanced by the increase in solubility from the temperature
increase due to adiabatic compression of the solution. 49 Understanding why a particular physical
form crystallises in the first place requires an understanding of both the thermodynamic stability
of the solid form and the kinetics of crystallisation. Understanding and modelling kinetic factors
is infinitely more difficult but is ultimately needed to fully master crystal form selection and
control.
Acknowledgments
Over the past five years my own work has been funded by the German Science Foundation, DFG,
Emmy Noether grant FA 9649/1-1 and has been facilitated by access to the ANKA and DESY
synchrotrons. I would also like to thank past and present collaborators for many fruitful
discussions. In particular, I would like to thank all my colleagues at the Georg-AugustUniversitt Gttingen for their continuous support. Special thanks go to current and former
group members: Sofiane Saouane, Rubn Granero-Garca, Lars Raue and Julian Holstein. The
work on Dalcetrapib was carried out in collaboration with Hidber Pirmin and Olaf Grassman (F.
Hoffmann-La Roche Ltd.), Jacco van de Streek (University of Copenhagen) and Marcus
Neumann (Avant-garde Materials Simulation Deutschland GmbH).
199
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201
Single Molecule Magnets
Single
moleculeand
magnets
Simon Parsons, School
of Chemistry
Centre for Science at Extreme Conditions, The
University of Edinburgh.
S.Parsons@ed.ac.uk Simon Parsons
School of Chemistry and Centre for Science at Extreme Conditions, The Univ. of
Edinburgh, Edinburgh, UK
S.Parsons@ed.ac.uk
www.cryst.chem.ec.ac.uk
Abstract
Single molecule magnets (SMMs) are materials which have the unusual property that they can
remain in a magnetised state after removal from a magnetic field. This is analogous to a bar
magnet, but at the scale of a single molecule, potentially making SMMs the smallest possible
entities for information storage. SMMs are usually large polymetallic complexes bound by Nand O- donor ligands. Their magnetic properties are very sensitive to structure, and since this
can be modified using pressure, parallel high-pressure crystallographic and magnetic
measurements are a powerful means for exploring magneto-structural relationships.
Keywords
Molecule-based magnets, single molecule magnets, structure-property relationships.

1. Introduction
Molecule-based magnets1 have numerous potential applications including magnetic sensors,
magnetic refrigerants, low density magnets, information storage devices and spintronic
materials. Use of molecular building blocks is advantageous because chemical derivatisation can
be used to modify or combine properties in a targeted way, and the ability to predict and control
the structural features which promote magnetic ordering is a key element in the design of
magnetic materials.
Pressure has little effect on intramolecular bond distances and angles in organic compounds,
though changes in torsion angles that occur during phase transitions can modify them slightly.
In the organic solid state the effects of pressure are therefore by-and-large restricted to
intermolecular interactions. The distinction between inter- and intra-molecular interactions is
not so clear-cut in transition metal complexes. Though changes in intermolecular interactions
certainly occur, substantial intramolecular structural modifications can also take place. These
include changes in metal-ligand distances; angular changes at bridging ligands; changes in spin
state and increases in coordination number. All of these changes affect magnetic coupling
between metal centres. This makes high pressure extremely attractive for investigating
magneto-structural correlations.
2. Magnetic Coupling
There is an extensive, and rapidly expanding, literature based on the synthesis and magnetic
properties of polynuclear transition metal complexes. The magnetic exchange between pairs of
202
metal centres in such complexes is characterised by coupling constants, J, the signs of which
determine whether a given interaction is ferro- or antiferromagnetic. Direct magnetic
exchange between metals involves overlap of the metal-based orbitals responsible for magnetic
properties (magnetic orbitals), and amounts to formation of a very weak metal-metal bond. It
has been suggested that this is the dominant mechanism in, for example, triply-bridged
dinuclear complexes of d3 metals.2 Direct exchange is characterised by the dependence of J on
the MM distance (r) of the type J r-n where n = 10-12.

A more common mechanism of coupling in metal complexes is superexchange, an indirect
process where the nature of a bridging ligand controls the relative orientations of the spins on
the metal centres. This interaction may be ferro- or antiferromagnetic, and is controlled by
geometry at the bridging ligand and the overlap integral of the magnetic orbitals on the metals.
The geometry of the bridge formed between two metal centres has an important influence on
the value of J, and a dependence of J on the bridging ligand is a characteristic sign of
superexchange. A simple model is shown in Fig 1. In a linear M-L-M bridge (Fig. 1a, where M is
a metal atom and L a bridging ligand) if the metal on the left is spin down, spin up electron
density will be donated from L, leaving spin down density to be donated to the metal on the
right, promoting a spin up configuration on the right-hand metal. The result is
antiferromagnetic coupling between the two metals. If the M-L-M bridge angle is 90 the metal
d-orbitals now interact with different p-orbitals on L. On the ligand it is energetically favourable
for electrons in different orbitals to align their spins parallel with each other, and so donation of
spin up electron density to one metal will promote donation of spin up density to the other.
This causes the spins on the metals to be aligned parallel, resulting in ferromagnetic coupling.
There are now numerous examples of magnetostructural correlations in dinuclear complexes
which define the relationship between J and the geometrical parameters associated with bridging
ligands.3
Figure 1. (a) Linear M-L-M geometry leads to antiferromagnetic coupling. (b) When the M-L-M angle approaches 90
coupling is ferromagnetic.
The important point here is that direct exchange and superexchange both depend on geometry,
and are therefore susceptible to modification with pressure. A relatively simple system where
both magnetic and single crystal diffraction data are available is Me4N[MnCl3], which has been
investigated up to 1.7 GPa.4 The system is composed of 1-D Mn(-Cl)3Mn((-Cl)3 polymers
203
(Fig. 2) separated by the cations. The strongest magnetic exchange processes in this system
occur within the chains, and the intrachain MnMn (antiferromagnetic) coupling constant
increased in magnitude from -6.85 to -7.81 K up to 1.7 GPa. The variation in J was correlated
with the MnMn distance, with an approximate r-10 dependence, implying the importance of
the direct mechanism for exchange.
3. Single molecule magnetism
Familiar bar magnets are able to retain their magnetisation because there is an energy barrier
towards reorientation of the magnetic moments of the metal centres as a result of the
ferromagnetic coupling between them. Certain polyoxometallic complexes are the subject of
intense research activity on account of their single molecule magnetism.5, 6 7 Below a blocking
temperature, typically a few K, single molecule magnets also retain magnetisation after removal
of a magnetic field, but whereas the magnetism of a bar magnet is a macroscopic effect, single
molecule magnetism occurs on the molecular scale.
Figure 2. One-dimensional chain formation in Me4N[MnCl3]. Coordinates taken from Cambridge Database entry
TMAMMN07.
Single molecule magnetism was first detected in the Mn12 complex [Mn12O12(OAc)16(H2O)4],
referred to as Mn12-acetate.8, 9 The complex consists of a central [Mn4O4] cubane-like core
containing Mn(+4), which is linked to a ring of eight Mn(+3) ions (Fig. 3).10 The crystal structure
is tetragonal (I4), with the complex on a 4 special position. The Mn(+4) ions are d3 with S =
3/2, while the Mn(+3) ions are high-spin d4 (S = 2) and exhibit a substantial Jahn-Teller
distortion.
Figure 3. The structure of Mn12-acetate. The three crystallographically unique Mn atoms are labelled. Mn1 is in the +4
oxidation state, Mn2 and Mn3 are in the +3 state. O-atoms are shown as open circles. The view is along [001], and the
complex has 4 symmetry. Disorder present in one acetate ligand is not shown.
204
The close-to-90 Mn-O-Mn bond angles within the cubane core of Mn12-acetate lead to
ferromagnetic coupling between the Mn(+4) sites. The interactions are between the Mn(+4) and
Mn(+3) are strongly antiferromagnetic, leading the Mn(+3) spins to align parallel with each
other, but in the opposite orientation to the spins on the Mn(+4) sites. The overall spin ground
state of the complex is therefore S = (8 2) (4 3/2) = 10.
Figure 4. Schematic spin state diagram for a single molecule magnet with an S = 10 ground state. Figure taken from ref.
11.
The S = 10 ground state in Mn12-acetate has 21 MS microstates with values of MS = 10, 90.
In the absence of a magnetic field these would normally be degenerate, but the presence of spinorbit coupling and the Jahn-Teller distortions of the Mn(+3) sites splits the energies of these
states with MS = 10 at one level, MS = 9 at the next level and so on. This is referred to as zero
field splitting, the magnitude of the effect being governed by the zero field splitting parameter D,
which is also referred to as the magnetic anisotropy parameter. The zero field splitting creates an
energy barrier to spin re-orientation, illustrated11 in Fig. 4. The height of the energy barrier (U)
is S2|D| if S is integral and (S2 )|D| for half-integral S. Single molecule magnetism requires
the energy barrier to be high, and this is achieved if the spin ground state S is high (e.g. 10 for
Mn12-acetate) and |D| is large. It is also important that D is negative, as this ensures that the MS
states are ordered so that MS = S have the lowest energy and MS = 0 the highest.
Figure 5. Energy level diagram for a single molecule magnet with ground-state spin S. (a) At equilibrium at RT, field off;
(b) magnetic field on at low temperature; (c) after removal of the field and return to RT. Figure taken from ref. 7.
205
The presence of the energy barrier shown in Fig. 4 enables the unusual properties of single
molecule magnets to be understood. At room temperature the MS = S (10 in Mn12-acetate) are
equally populated (Fig. 5a).7 Application of a magnetic field changes the energy levels as shown
in Fig. 5b, and if the temperature is low enough only the MS = S level is populated. Removal of
the magnetic field re-establishes the energy levels of Fig. 5a, but if the temperature remains low
the spins lack the thermal energy required to cross the energy barrier (i.e. to reorient): the
system is trapped in the S level and the overall magnetisation is retained. If the temperature is
raised the population of the MS = +S level is be re-established (Fig. 5c) and the magnetisation
lost: this is why single molecule magnetism is a low-temperature effect.
The value of S can be obtained by measuring the magnetic susceptibility (M) against
temperature in a SQUID magnetometer. The value of MT increases to a value of 51 cm3 K mol1
at 15 K. The ideal value for S = 10 is 55 cm3 K mol1 [= S(S + 1)].12 The value of D can be
measured with high-field electron paramagnetic resonance or by measuring magnetisation
against temperature at different field strengths. For Mn12-acetate D is 0.457(2) cm1. 12 13 These
values give U = 46 cm1, more commonly expressed in units of K as U/kB = 66 K (where kB is
Boltzmanns constant; 1 K = 0.695 cm1). If the barrier height is obtained directly using ac
susceptibility measurements, a slightly lower value, 62 K, is obtained which reflects some degree
of reorientation by tunnelling through the energy barrier shown in Fig. 4. Single molecule
magnet behaviour can also be characterised using hysteresis loops measured at low temperature,
which have a step-like rather than smoothly varying appearance, which is also owed to the
effects of tunnelling.
B
4. The effect of pressure on Jahn-Teller isomers in derivatives of Mn12-acetate14
The high value of |D| for Mn12-acetate arises because of the near alignment of the Jahn-Teller
axes of the eight Mn(+3) ions with the crystallographic c-direction (perpendicular to the page in
Fig. 3). Certain derivatives of Mn12-acetate exhibit misalignment of some of the Mn(+3) JahnTeller axes causing the energy barrier to become smaller. Complexes with alternative
arrangements of the Jahn-Teller axes are referred to as Jahn-Teller isomers.6 Jahn-Teller isomers
exist in low concentration in samples of Mn12-acetate itself, and the energy barrier is 40 K for
these species, which are referred to as fast-relaxing (FR) isomers to contrast them with the
majority slow-relaxing (SR) species.15
The Mn12 derivative [Mn12O12(O2CCH2tBu)16(H2O)4]CH2Cl2MeNO2 possesses a similar
structure to Mn12acetate, except that one Mn(+3) site is bound to two water molecules.6, 16
Unlike Mn12acetate, compound 1 has only seven vertical Jahn-Teller bonds at 150 K and
ambient pressure. In the eighth Mn(+3) site, labelled Mn8, Mn-O distances in the horizontal
plane of the complex are 2.049(2) and 2.145(3) , where the other Mn-O distances lie between
1.893(3) and 1.961(2) (Fig. 6, Table 1). At room temperature all six Mn-O distances span
1.930(4)-2.025(4) , the lack of a clear Jahn-Teller axis suggesting disorder.14
206
The unusual arrangement of the ligands about Mn8 is the result of subtle crystal packing effects,
and if the sample is allowed to de-solvate, or if a solvate with CH2Cl2.MeCN is formed, the
normal isomer is obtained.6, 16 The crystal packing effects can also be modified with pressure. On
application of pressure, the main structural changes within the cluster occur at the Mn(+3)
centres. At 1.5 GPa, the Jahn-Teller elongated bonds on the normally-distorted centres either
become more unsymmetrical, or decrease by an average of 0.02 . At the isomersied centre the
range of Mn-O distances increases to 1.94(2) to 2.082(15) , suggesting that the disorder present
at ambient pressure persists. At 2.5 GPa, the behaviour at the isomerised centre is clearer, with
vertical Mn-O distances of 2.105(17) and 2.19(2) and in-plane distances spanning 1.88(3) to
2.03(3) , indicating that the horizontal Jahn-Teller bonds at ambient pressure have switched to
vertical Jahn-Teller bonds at 2.5 GPa. Between 1.5 and 2.5 GPa, the Jahn-Teller bonds on the
remaining centers do not change significantly. Release of pressure re-establishes the
coordination seen at ambient pressure.
Figure 6. Atom labelling and orientation of the principal components of the strain tensor superimposed on the
coordination sphere of the Jahn-Teller isomerised centre Mn8 in [Mn12O12(O2CCH2tBu)16(H2O)4]-CH2Cl2MeNO2.
The ac susceptibility was measured from ambient pressure to 1.44 GPa and this also shows
conversion from the fast relaxing to the slow relaxing species (Fig. 7a). The ambient pressure
data reveal only one peak at low temperature (Tmax = 2.1 K at 1 Hz) due to the fast relaxing
species: there is no slow relaxing isomer present. At 0.47 GPa, the low temperature peak shifts to
slightly higher temperature (ca. 2.3 K) and decreases in intensity. At the same time a broader
peak appears at around 4 K, indicating that both the fast relaxing and slow relaxing species are
present. Only the high temperature peak is present at 1.44 GPa (Tmax = 4.1 K at 1 Hz) due to the
exclusive presence of the slow relaxing species. Frequency-dependent ac data indicate that U/kB
for the fast-relaxing species is 41 K, increasing to 46 K at 1.12 GPa. The energy barrier of the
pressure-induced SR species is 63 K at 0.47 GPa, and the value is unchanged at 1.12 GPa. The
corresponding widening of the hysteresis loop with pressure is shown in Fig. 7b. Release of
pressure re-establishes the fast-relaxing species.
B
207
The ac susceptibility data are thus consistent with the high-pressure structural data, the slightly
different switching pressure likely being due to the diffraction study being carried out at ambient
temperature whereas the magnetic study is carried out below 10 K.
150 K/0 GPa
RT/0 GPa
RT/1.5 GPa
RT/2.5 GPa
RT/0GPa
Mn8-O108
1.893(3)
1.930(4)
1.98(2)
1.88(3)
1.932(4)
Mn8-O13
1.963(3)
2.002(5)
2.02(3)
1.89(3)
1.994(4)
Mn8-O208
2.049(2)
1.966(4)
1.94(2)
1.90(3)
1.956(4)
Mn8-O25
2.145(3)
2.025(4)
2.04(3)
2.03(3)
2.022(5)
Mn8-O14
1.961(2)
2.012(5)
2.082(15)
2.105(17)
2.015(5)
Mn8-O26
1.956(3)
2.010(5)
2.034(17)
2.19(2)
2.005(5)
Table 1: Distances () around Mn8 in [Mn12O12(O2CCH2tBu)16(H2O)4]-CH2Cl2MeNO2.
Bold = significantly elongated.
The strain tensor,17 which can be calculated from the changes in unit cell dimensions with
pressure, expresses the overall effect of pressure on a crystal structure, revealing the directions
which undergo the greatest and least compression. When the two largest components of strain
are superimposed on Mn8 they are found to lie in the horizontal plane containing the JahnTeller axis at ambient pressure (Fig. 6). The effect of pressure is therefore to compress the local
structure around Mn8 most in the horizontal direction, pushing the Jahn-Teller axis into the
normal vertical orientation. The new orientation of the Jahn-Teller axis also corresponds to the
direction of the smallest strain component.
Figure 7. (a) Conversion of the fast- (FR) to the slow-relaxing (SR) species: evolution of the out of phase ac susceptibility
for [Mn12O12(O2CCH2tBu)16(H2O)4]CH2Cl2MeNO2 under pressure, measured at a fixed frequency of 1 Hz. (b) 4
Evolution of the hysteresis loops of 1 at 2 K, from ambient pressure to 1.44 GPa.
The principal axial directions of the strain tensor depend on how the molecules are packed (Fig.
8). The smallest component of strain points directly at a neighbouring molecule, and presumably
this is why compression is most restricted in this direction. By contrast, the two largest
components point between neighbouring molecules, making compression energetically more
favourable in these directions.
208
Figure 8. The relationship between principal axes of the strain tensor and crystal packing in
[Mn12O12(O2CCH2tBu)16(H2O)4]CH2Cl2MeNO2.
5. The effect of pressure on ferromagnetic coupling in [Mn6] single molecule magnets18
The [Mn6] family of single molecule magnets which have general formula [Mn6O2(Rsao)6(RCO2)2(L)4-6] (where sao2- is the dianion of salicylaldoxime). All the Mn centres are in the
+3 oxidation state. One member of the family, [Mn6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6] (Fig. 9a),
has one of the highest energy barriers (83 K) towards reorientation of any single molecule
magnet.19-24 The high energy barrier depends on maximising ferromagnetic interactions
between the metal centres.
The spin ground state of [Mn6] clusters can be controlled via a structural distortion imposed by
the steric requirements of the salicylaldoxime ligands. For Mn-N-O-Mn torsion angles greater
than 31 the pairwise exchange between the Mn ions switches from antiferromagnetic to
ferromagnetic.20 This conclusion was based on the magnetic properties of different derivatives
of [Mn6], with the assumption that changes of ligand and solvent of crystallisation play no role.
Studying the evolution of magnetic behaviour with pressure avoids the need to make this
assumption because the same complex can be studied as a function of increasing structural
distortion.
The complex [Mn6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6] is centrosymmetric, consisting of two
Mn3(3-O) triangular subunits linked via two oximate O-atoms and two phenoxide O-atoms.
The bridging between neighbouring Mn ions within each triangle occurs through an NO
oximate group, such that each Mn2 pair forms a -Mn-N-O-Mn- moiety (Fig 9a). At ambient
pressure all the Mn-N-O-Mn torsion angles around the triangles are 42.9(5), 39.1(5) and
34.8(6). These are all above 31, and dc magnetic susceptibility data were modelled with
ferromagnetic coupling between all bridged MnMn pairs. At 1.5 GPa the torsion angles
became 44(2), 34(2) and 28(2). One of these angles is less than 31, and accordingly modelling
209
of magnetic susceptibility data also collected at 1.5 GPa required introduction of

antiferromagnetic coupling between the Mn atoms linked by this interaction, confirming the
proposed correlation based on the Mn-N-O-Mn torsion angle.
At ambient pressure the angles made with the Mn3 planes by the Jahn-Teller axes of the Mn
atoms in [Mn6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6] span the range 84.6-89.8, while at 1.5 GPa
they span 87.3-89.5. The more parallel alignment would be expected to increases the magnetic
anisotropy (D) of the complex, and indeed this changes from 0.38 cm-1 at ambient pressure to
0.44 cm-1 at 1.5 GPa.
When pressure is applied to [Mn6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6] there are thus two counteracting effects on the effective energy barrier to reorientation of the magnetisation. Although the
spin of the ground state at 1.5 GPa is the same as at ambient pressure (S = 12), the introduction
of antiferromagnetic coupling reduces the energy difference between the ground state and the S
= 11 and 10 excited states. These are thought to play an important role in facilitating magnetic
relaxation by tunnelling processes, reducing the effective energy barrier to reorientation. The
increase in the magnitude of the anisotropy acts to increase the energy barrier. Of these two
effects the first wins. The energy barrier reduced from 83 K at ambient pressure to 45 K at 1.5
GPa, an effect illustrated hysteresis loops measured as a function of pressure (Fig. 9b).
Figure 9. (a) Molecular structure of [Mn6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6]. Coordinates taken from Cambridge

Database entry CEYMAV; carbon atoms are shown in framework format, and hydrogen atoms not involved in Hbonding have been omitted for clarity. (b) Hysteresis loops measured as a function of pressure (1 GPa = 10 kbar).
210
Acknowledgements
The results described in Sections 4 and 5 were obtained as part of a collaboration with Professor
Euan Brechin, Professor Konstantin Kamenev and Dr Mark Murrie and their groups at the
Universities of Edinburgh and Glasgow. The high-pressure crystallographic and magnetic work
was carried out by Drs Stephen Moggach, Pascal Parois, Alex Prescimone and Javier SanchezBenitez. The project was funded by the EPSRC, with generous allocations of beamtime at STFC
Daresbury Laboratory and Diamond Light Source and outstanding support by beamline
scientists Dr John Warren and David Allan.
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Parsons and M. Murrie, Chem. Commun. (Cambridge, U. K.), 2010, 46, 1881-1883.
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Communications, 2003, DOI: 10.1039/B306246E, 2672-2673.
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Bircher, M. Murrie, S. Parsons and E. K. Brechin, Angew. Chem., Int. Ed., 2008, 47, 2828-2831.
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212
Pair Distribution Function Analysis
Pair distribution
function
analysis
Karena
W. Chapman,
X-ray Science
Division, Advanced Photon Source, Argonne National
Laboratory, Lemont, Illinois, 60439, USA
Karenachapmank@aps.anl.gov
W. Chapman
email:
X-ray Science Division, Advanced Photon Source, Argonne National Laboratory,

Lemont, IL, USA
chapmank@aps.anl.gov
www.aps.anl.gov/About/People/Detail/?name=Karena__Chapman
Abstract
In the last decade, the atomic Pair Distribution Function (PDF) methodology has transformed
from a niche analysis practiced by a handful of experts to a broadly useful tool capable of
addressing complex problems in chemistry, physics, material science and geology. PDF probes
local material structure with crystallographic-resolution, but is not limited to crystalline
materials, as are required for conventional Bragg analysis. Accordingly PDF can probe the
structure-function relationship in wide-ranging materials including crystalline, disordered,
amorphous, nanoscale, and heterogeneous systems. Advances in experimental approach,
detector technologies and the construction of dedicated PDF instruments at large user facilities,
have increased availability of quantitative PDF data, transforming the science and problem
complexity that can be addressed by PDF. One no longer needs to model a single, precious PDF
to extract every insight possible. Instead, one can undertake systematic studies as a function
environmental variable (including pressure), reaction state or composition.
Keywords
Total scattering, Diffuse scattering, High Energy X-rays, Nanomaterials, Amorphous

Introduction
Pair Distribution Function (PDF) analysis has grown to become a valuable tool to probe the local
atomic structure of materials. It provides a wide range of local structural information, with
crystallographic resolution, for broad classes of materials.1 This includes for nanoscale materials
or amorphous, liquid, or gaseous phases, for which conventional Bragg analysis fails.
The structural information in the PDF is available as a weighted histogram of all atomatom
distances within a material. It is a function in real-space, G(r), where peaks indicate an increased
probability of finding atoms at a particular distance r, the characteristic interatomic distance or
bond length (Figure 1).
Experimentally, the PDF is derived from scattering data, from a specialized powder diffraction
measurement. It is the Fourier transform of the total structure factor that is related to the
coherent part of the scattering intensity from an x-ray or neutron scattering measurement. The
analysis, alternatively referred to as total scattering analysis, utilizes both Bragg and diffuse
contributions to the scattering, following correction of the measured data for background and
inelastic scattering contributions. That a PDF is related to the experimental total scattering data
213
via a Fourier transformation gives rise to practical challenges that, until recently, had limited
applications PDF.
Figure 1. A pair distribution function, G(r), derived from high-energy x-ray total scattering, provides real-space
structure information independent of structure modeling. Note: r, interatomic distance.
While the formalism behind the PDF methodology was established ~90 years ago (see Figure 2),
not long after the foundation of crystallography) the experimental challenge in collecting data to
high values of Q, until recently, prevented widespread application of the methodology. With
limited data quality and access, PDF was, for the most part, a specialized tool used by experts.
Applications were focused on static studies of relatively simple material compositions at ambient
condition.
Figure 1. A brief history of pair distribution function measurements. Gains have been made through the advent of
computers to perform the Fourier transformation, large synchrotron and spallation sources of intense x-ray and neutron
beams, and, most recently, the combination of high-energy x-rays from large third-generation synchrotron sources with
large area detectors.
Since the early 2000s, advances in experimental approach, instrumentation, and detector
technologies have increased access to PDF data, providing improved data quality in substantially
reduced measurement times.2 The expanded access to high-quality, quantitative PDF data has
214
changed the types of materials, experiments, and the questions that can be answered using PDF.
Accessibility to data provides new opportunities: more data allows for more ways to approach a
question. It has now become possible to conduct quantitative PDF measurements with high
sensitivity to probe weakly scattering or dilute species, with fast time resolution to capture
dynamic states and reactions, or in an ever expanding range of non-ambient sample
environments to explore structure as a function of an environmental variable or under operating
conditions. Multiple data sets, collected for series of materials or for a single material system
under different conditions, can be leveraged to gain new insights, including model-independent
structural parameters derived directly from the PDF. This has opened the door to studying more
complex systems. We can now characterize more complex heterogeneous materials, recover
chemical sensitivity, undertake detailed in situ or operando studies, use direct insights from realspace features in the PDFs to address questions relevant to diverse scientific fields.
Formalisms and Definitions
The PDF is related to the probability of finding a pair of atoms at a given radial distance, r.
Historically, various nomenclatures and related definitions have been used to describe this type
of atomic correlation function. This includes the term radial electron distribution, RED, the total
correlation function, T(r), and the radial distribution function, R(r). A complete description of
the different atomic correlation functions can be found in Keen et al.3 and the mathematical
foundation underlying PDF analysis has been described in detail by Warren in his book X-ray
Diffraction4 and, more recently, by Egami and Billinge in Underneath the Bragg Peaks.5
The form presented here, which is widely used, is G(r), which is rigorously known as the reduced
pair distribution function. It is defined as,
G(r) = 4r[(r)- o] = 4ro(g(r)-1)
(1)
where r is the interatomic distance, o is the average number density and (r) is the local number
density,[25-26]
(r) = o[g(r)]
(2)
This incorporates the function g(r), the direct probability of finding two atoms at a distance r.
It has the advantage of this form of the PDF is that G(r) can be directly derived from the
experimental data. It is the sine Fourier transform of the reduced structure function, S(Q) which
can be measured through a scattering experiment,
G(r) = 2/ Q[S(Q)-1]sin(Qr)dQ
(3)
where Q is momentum transfer, a function of scattering angle() and wavelength (),
Q = 4 sin()/
(4)
215
The structure factor, S(Q),

S(Q) = 1 + [Icoh(Q) - ci|fi(Q)|2]/|cifi(Q)|2
(5)
is related to coherent part of the diffraction intensity, Icoh(Q), which including both Bragg and
diffuse contributions, that is, the total scattering intensity. The Icoh(Q) is determined
experimentally, as part of a scattering experiment, correcting the measured intensities for
background contributions, measurement/detector effects, Compton scattering and other
inelastic processes (e.g. fluorescence).
The form of G(r) has several distinct characteristics: G(r) oscillates about zero for large values of
r; G(r) approaches 0 as r0 where it behaves as -4or. Accordingly, at low r, this function is a

straight line through 0, with slope that is proportional to the average number density of the
material, o.
Structural Insights from PDF data
The PDF describes atomic structure on the local and intermediate length scales extending from
the local coordination environment up to several nanometers. In many ways the structural
information available from a PDF measurement is analogous to insights from EXAFS, diffraction
and SAXS studies. The structural information in the PDF is obtained as a histogram of the
distance between all pairs of atoms within a material. This is weighted by the scattering power
and the relative abundance of that atom pair.
Peaks in the PDF indicate an increased probability of finding atoms at a particular distance r,
that is, a characteristic interatomic distance or bond length within the material. The
coordination number is related to the area of a peak. The peak width provides insight into the
distribution of similar distances, that is, disorder. The highest distance at which peaks are
observed is related to the size of a particle or coherent domain. Structural insights can be derived
directly from the features in the PDF, structure models can also be refined against the data, and
the data can be used to benchmark computational simulations.
Direct structural insights from PDF data
A wealth of information can be obtained directly from particular features in the PDF, even
without need for a structure model (see Figure 1).
The position of peaks in the PDF corresponds directly to the bond lengths and atomic
distances within a material. Determining the position of a peak, for example, through fitting of
a Gaussian function, provides an accurate measure of the atomic distances. In contrast, the
peaks evident in an EXAFS analysis must be corrected for the phase shift, through
development of a structure model, to determine the bond length. Furthermore, in the PDF,
longer atomic distances can be readily determined. The atomic distances can be used to derive
accurate coordination geometries, to develop structure models or may be used to identify
changes in oxidation state.
216
The area of a peak in the PDF is proportional to the abundance of the associated atom pair.
By quantifying changes in peak area, for example, through fitting of a Gaussian function,
changes in the abundance of the correlation can be monitored. For a well-defined cluster,
molecule, or polyatomic ion, the peak area is directly correlated to concentration. For
nanoparticles, the peak area is additionally linked to particle size, with the average number of
nearest neighbors decreasing for small particles with a higher surface area to volume ratio.
This effect, however, is less pronounced for larger nanoparticles (beyond ~2 nm) than for
small clusters. By evaluating the changes in peak area and, accordingly, species concentration
though a transformation/reaction can be accurately determined.
Well defined features in the PDF exist in the range over which the material is well ordered.
Thus for bulk, crystalline systems, where the material is ordered to long length scales, well
defined features persist to high r (essentially infinite r, although in practice this is ultimately
limited by instrument/experimental resolution). In contrast, for amorphous or nanoscale
systems, where structural order exists over a finite range, peaks are only clearly defined over
the ordered domain. Consequently, the maximum distance r at which well-defined peaks are
evident in the PDF provides an indication of the dimensions of nanoparticles or the ordered
domain size in amorphous systems. This can be modeled quantitatively using a spherical
particle envelope. Maximal particle dimensions up to ~10 nm can be accurately determined
with no lower size limit. The insights into nanoparticle size are similar to those available from
a SAXS analysis, although for larger nanoparticles SAXS analysis provides greater accuracy.
The slope of the PDF at low r is related to the material density.
By monitoring changes to particular features during in-situ studies, detailed insights can often be
derived including changes in concentration or atomic structure. The large quantity and highly
consistent nature of data possible using in-situ methods is key to enabling these type of studies
and allows quantitative insights and correlated parameters to be identified directly from the PDF
data.
Structural insights from modeling PDF data
Separate to the insights that can be obtained directly from the PDF data, structural models can
be tested or refined against the PDF data to determine the structure of the catalyst and how it
may change under reactive conditions. Different approaches have been established to model
PDF data. In modeling the data, it is possible to select the r-range of the PDF used in the
refinement, to focus on structural ordering over particular length scales. Further, based on
models, it is possible to calculate the contributions to the PDF from different atom pairsthe
partial PDFswhich can be valuable in identifying the origin of structural perturbations. Several
programs are widely used to model PDF data including PDFgui6.
A real space analogue to Rietveld analysis of powder diffraction data is the most common
approach to modeling PDF data. This applies periodic boundary conditions to a single unit
cell. Atomic positions are subject to space group symmetry constraints, atomic displacement
217
parameters model static and dynamic disorder and a spherical particle envelope function
models the average dimension of nanoparticles or lengthscale of structural coherence in
disordered systems. Models are optimized through least squares methods. This approach can
be used to identify and quantify phases, refine atomic structure and stoichiometry, and
estimate particle size, including for nanoscale systems where size broadening of Bragg peaks
limits the crystallographic analysis. This can be applied to bulk phases and nanoscale materials;
however, this approach has limited ability to model discrete clusters or surface binding
interactions. Note: the absolute value of the R-factors obtained from fits to PDF data are larger
than conventional Rietveld fits of comparable quality, as to obtain the PDF, the scattering data
are multiplied by a factor of Q, thus amplifying the noise.
Extended models derived from multiple independent unit cells with periodic boundary
conditions, not subject to symmetry constraints, can be optimized using Reverse Monte Carlo
algorithms. This can be applied where the local defects or distortions cannot be described
within a simple unit cell model. These models are often under constrained by the PDF data
and can benefit from additional constraints from complementary data (e.g. local structure
constrains from EXAFS or NMR).
Structural models developed through computational simulations can be readily evaluated
against experimentally obtained PDF data.
Explicit atomistic models of discrete clusters or whole nanoparticles and ensembles of
nanoparticles can be constructed.
Differential PDF Analysis
While not intrinsically an element, chemical or surface specific probe, by extending the PDF
experiment to measure one or more additional related systems, such specificity can be recovered
and insights greatly enhanced. Specifically using a differential analysis, the PDF data are treated
to focus on particular species or features within the sample (Figure 3).7 As the PDF is summed
over all interatomic distances within a material, the contributions from multi-components
systems are purely additive. Consequently, if the PDF from one component can be explicitly
measured, this reference PDF can be subtracted from the total PDF for the multi-component
system, thus isolating the contribution from the second component, as well as any well-defined
inter-component interactions. The differential PDF can then be analyzed as described
previously.
218
Figure 3. A differential approach to PDF analysis. As PDF contains contributions from all atom-atom distances within a
material, it can be difficult to directly identify contributions from species of interest, particularly for dilute systems. A
differential approach can be used to recover chemically specific PDF information. In this case, for 1wt% Pt nanoparticles
on -Al2O3, a reference PDF measured for the -Al2O3 support alone can be subtracted from the total PDF to yield the
differential PDF which isolate contributions from supported Pt particles (as well as any well-defined Pt-support
interactions).8
In principle, a differential PDF can be obtained by subtraction of I(Q) or direct subtraction of the
PDF itself. The advantage of obtaining the differential PDF by subtracting the PDFs, rather than
calculating the difference in the scattering intensity I(Q) before the Fourier transform, is that any
artifacts in the PDF data are generally consistent between the total and reference PDF such that
they cancel in the differential PDF. Notably, features at low r, where any artifacts in the PDF data
are most pronounced, e.g. from errors in normalization or the truncation of the Fourier
transform, can be readily distinguished. This allows reliable analysis of dilute components within
the system with demonstrated sensitivity to components at the 1 wt% level and below.
In this way, and through careful experiment design and reference measurements, chemical
specificity or surface sensitivity can be derived. While EXAFS offers intrinsic element specificity,
explicitly only probing a single element within the sample, the differential approach to PDF is
more broadly applicable, and not limited to systems with suitable absorption edges.
PDF measurements: Considerations & Challenges
The PDF is obtained experimentally from a scattering measurement. Being related to the
scattering data via a Fourier transform, the resolution of the PDF depends on the Q-range
measured and used in the Fourier transform (Figure 4). Thus, S(Q) must be measured to a high
value of Q, typically > 20 -1 for crystalline materials. The finite Q-range that is adequate
depends on the magnitude of the Debye-Waller factor. The contributions from the termination
ripples, that arise from Fourier transform over a finite Q-range, are more pronounced, that is,
have greater relative intensity and lower periodicity (given by 2/Qmax).
219
Figure 4. A quantitative, high resolution PDF requires that S(Q) is Fourier transformed over a wide range of Q. This
series of PDFs calculated for Ni metal using different maximal values of Q, demonstrates that Qmax > ~20 1 is needed to
ensure that the peaks due to atom-atom correlations can be readily distinguished from artifacts in the data (e.g.
termination ripples).
Typical laboratory-based diffraction instruments (equipped with a Cu-K x-ray generator), only
routinely collect scattering data to Qmax ~ 68 1. High energy X-rays and neutrons (from a
spallation or hot source) provide access to a suitably large Q-range for quantitative PDF data.
The higher X-ray fluxes and wider range of sample environment, make these more readily
amenable to in-situ and time-resolved measurements. The Advanced Photon Source, the
synchrotron storage ring located at Argonne National Laboratory, is one of the worlds brightest
sources of high energy X-rays and home to the first dedicate X-ray PDF instrument, 11-ID-B.
A modern X-ray PDF experiment is essentially a specialized powder diffraction measurement in
transmission geometry.2 High energy X-rays (>50keV) are used to compress a broad Q-range of
X-ray scattering data into a finite 2-theta range defined by the detection surface of a large twodimensional detector. This detector is oriented perpendicular to the incident beam, and
positioned a short distance from the sample (10-40 cm), to maximize the 2-theta range (and Qrange) intersected by the detector (Figure 5). Using this approach, all data for an individual PDF
is collected simultaneously, such that data rate and measurement times are only limited by the
signal-to-noise ratio and the read out rate of the detector. Measurement times have been
reduced by several orders of magnitude compared to traditional experimental approaches to Xray PDF measurementsfrom hours to minutes or seconds. Historically, X-ray PDF
measurements have used 2-theta scans of a point counting detector, typically requiring ~ 12
hours to accumulate sufficient counting statistics at each point. The solid detector angle afforded
by the area detector provides increasing counting statistics at higher angles (where the X-ray
form factor makes improved statistics most beneficial). The area detectors used for modern PDF
measurements do not discriminate based on X-ray energy as was previously achieved using an
analyzer-equipped scanning point counting detector. Consequently, the inelastic Compton
220
scattering is measured and must be accurately calculated based on the known sample
composition and subtracted from the measured intensities.
Figure 5. Modern x-ray pair distribution function (PDF) measurements use a transmission geometry set up where highenergy x-rays compress a wide Q-range into a small angular range that is intersected by a large area detector placed close
to the sample. This configuration has reduced data acquisition times from ~ half-day to less than a seconds-per-PDF.
The PDF data shown here, and accompanying schematic structure, is for amorphous SiO2 with Si shown in blue and
oxygen in red.
The scattering measurement must be accurately corrected for background scattering (measured
for the empty sample holder or sample environment), incoherent (Compton) scattering, multiple
scattering and fluorescence. Errors in these corrections, for example from ambiguity in the
sample composition (and accordingly the Compton scattering correction), produce slowly
varying errors in S(Q), which in the Fourier transformed PDF are apparent as artifacts at low r,
that is, at unphysical distances (e.g. below r ~ 1 ). In practice the magnitude of these low r
artifacts provide an indication of the accuracy of the data correction and PDF data.
For quantitative PDF data from in-situ or non-ambient experiments, a sample environment must
provide access to wide scattering angles and Q-range. Scattering from the sample environment
itself must by highly reproducible and ideally low, such that the background scattering can be
independently measured and subtracted to recover the total scattering data from the sample.
PDF measurements at high pressure
While PDF methods are well suited to the study of pressure-dependent phenomena, including
for nanomaterials and glasses, and amorphous-to-amorphous, crystalline-to-amorphous and
other structural transitions, PDF studies at high-pressure are an experimental challenge.9 This is
due to the divergent requirements of high-pressure sample environments and PDF
measurements:
Devices utilized to generate high pressures for in situ scattering measurements, e.g., diamond
anvil cells (DACs), use small, highly encapsulated samples, resulting in low sample-tobackground scattering ratios (Figure 6). In contrast, high quality PDFs benefit from high
sample-to-background and signal-to-noise ratios.
While empirical background treatments are typical for Bragg crystallographic analyses, PDF
measurements benefit from a very accurate background correction.
221
High-pressure cells such as DACs limit angular access for the incident and scattered X-ray
beams and ultimately defines the Q-range that can be measured. While this is not generally
problematic for Bragg crystallographic analyses, which rely heavily on the data at low
scattering angles, high-quality PDFs require access to large scattering angles to measure data
to high values of momentum transfer, Q. High-energy X-rays to concentrate the scattering
into a smaller solid angle and thereby facilitate access to a wide Q-range. However, highenergy X-rays can be difficult to focus as needed for DAC measurements.
Fig. 6: (left) Scattering intensities measured with an empty DAC, an -Al2O3 sample-loaded DAC and without a DAC in
the beam. The diamond scattering is the largest contribution to the measured intensity. (right) Part of a scattering image
measured for an empty diamond cell, outlining the regions of diffuse and Bragg scattering that must be masked.
The large contribution of the diamonds to the measured scattering data, and the unfeasibility of
directly measuring the contribution from the cell to the background are the principal challenges
in acquiring high pressure PDF data within a DAC.
The single crystal diamond windows on the DAC contribute significantly to the measured
scattering, including two sets of single crystal Bragg reflections, structured single crystal diffuse
scattering (thermal and strain-induced) predominately localized around the Bragg peaks, and the
radially-symmetric Compton scattering. The structured (Bragg and diffuse) contributions
change as a function of pressure due to variability in the diamond position, and strain generated
in the diamonds at pressure. As it is not feasible to measure the scattering of the empty cell as a
function of pressure, it is essential to exclude pressure-dependent contributions to the
background scattering. This can be achieved by "masking" the Bragg peaks and structured diffuse
scattering before reducing the images to one-dimensional diffraction patterns. While it is not
always straightforward to directly identify the regions of diffuse diamond scattering that must be
masked (Figure 6), strategies have been developed to reliably construct such a mask.9
222
Figure 8. (left) The scattering geometry for background from the diamond anvils and how this is limited by absorption
by the cell body. (right) Simulated changes in the background scattering due to this attenuation as the sample thins and
the diamond shifts under pressure.
As a further complication, while the background is measured for the empty cell at ambient
pressure, as the pressure is increased, the sample/gasket progressively thins, changing the
relative position of one of the diamonds relative to the cell body. This changes where the
background scattering from the diamonds is partially attenuated by the cell body (Figure 7),
impacting the useable angular range.
While PDF measurements at high pressure are challenging, with appropriate selection of
instrument configuration, pressure cell configuration and data reduction strategies, high quality,
quantitative PDF data can be successfully acquired.9
Conclusions
As PDF analysis no longer being limited by access to high-quality data, the experimental
frontiers of the methodology have shifted to the development of new in-situ, non-ambient and
operando measurements. With major upgrades planned for experimental user facilities such as
the Advanced Photon Source at Argonne National Laboratory in the USA, Diamond Light
Source in the UK and the European Synchrotron Radiation Facility and the construction of new
dedicated PDF instruments the future of the methodology is bright.
Acknowledgments
Use of the Advanced Photon Source, an Office of Science User Facility operated for the US
Department of Energy Office of Science by Argonne National Laboratory, was supported by the
US Department of Energy under Contract No. DE-AC0206CH11357.
References
Chapman KW. Emerging operando and x-ray pair distribution function methods for energy materials
development. MRS Bull 41, 231-240 (2016).
Chupas PJ, Qiu X, Hanson JC, Lee PL, Grey CP, Billinge SJL. Rapid-acquisition pair distribution function
(RA-PDF) analysis. J Appl Crystallogr 36, 1342-1347 (2003).
Keen D. A comparison of various commonly used correlation functions for describing total scattering. J
Appl Crystallogr 34, 172-177 (2001).
Warren BE. X-ray Diffraction. Dover (1990).
223
Egami T, Billinge SJL. Underneath the Bragg Peaks Structural Analysis of Complex Materials. Pergamon
(2012).
Farrow CL, et al. PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals. J Phys:
Condens Matter 19, 335219 (2007).
Chapman KW, Chupas PJ, Kepert CJ. Selective Recovery of Dynamic Guest Structure in a Nanoporous
Prussian Blue Through in situ X-ray Diffraction: a Differential Pair Distribution Function Analysis. J Am
Chem Soc 127, 11232-11233 (2005).
Chapman KW, Chupas PJ. Pair Distribution Function Analysis of High-Energy X-ray Scattering Data. In:
In-situ Characterization of Heterogeneous Catalysts (John Wiley & Sons, Inc. (2013).
Chapman KW, et al. Optimizing high-pressure pair distribution function measurements in diamond anvil
cells. J Appl Crystallogr 43, 297-307 (2010).
224
Pressure-induced amorphization
Pressure-induced
amorphisation
Denis
Machon, Institut
Lumire Matire, UMR5306 Universit Lyon 1-CNRS, Universit de
Lyon - 69622 Villeurbanne cedex, France
Denis denis.machon@univ-lyon1.fr
Machon
email:
Inst. Lumire Matire, UMR5306 Universit Lyon 1-CNRS, Villeurbanne, France

denis.machon@univ-lyon1.fr
Abstract
Pressure-Induced Amorphization (PIA) occurs as a crystalline solid is compressed beyond its
normal stability range at a temperature too low or on a rapid timescale so that expected
crystalline phase transformations cannot be initiated or completed. It was first reported for ice
Ih in 1984 following prediction of a metastable melting event associated with the negative initial
melting slope observed for that material. Further examples of PIA were observed and interpreted
as the result of instabilities. The superpressed crystal may encounter an intrinsic elastic or
mechanical stability limit or it may develop a critical concentration of defects so that it
transforms into an amorphous version of the same substance.
Keywords
Amorphous, thermodynamics, kinetics, nanocrystals

Introduction
Pressure-induced amorphization (PIA) is a phenomenon that involves an abrupt transition

between a crystalline material and an amorphous solid through application of pressure at
temperatures well below the melting point or glass transition range. It was first reported for ice
Ih in 1984 following prediction of a metastable melting event associated with the negative initial
melting slope observed for that material 1 . The unusual phenomenon attracted intense interest
and by the early 1990s PIA had been reported to occur among a wide range of elements and
compounds 2, 3 , 4 , 5 .
However, with the advent of powerful experimental techniques including high resolution
synchrotron X-ray and neutron scattering combined with more precise control over the
pressurization environment, closer examination showed that some of the effects previously
reported as PIA were likely due to formation of nanocrystals, or even that PIA was completely
bypassed during examination of single crystals or materials treated under more hydrostatic
compression conditions. It is important to recognize that PIA along with all other metastable
structural transformations occurring during low temperature compression or on a rapid
timescale, is subject to kinetic effects that hinder bond-breaking and -reforming processes as
well as atomic or ionic diffusion that would lead to an equilibrium ordered state. In addition, the
distribution of applied stresses external to or developed within the sample is important, as
deviations from truly isotropic or hydrostatic compression can provide lowered energy pathways
225
or local driving forces leading to PIA. Slower compression of single crystals under quasihydrostatic conditions results in metastable crystalline transformations, whereas compression of
powders under non-hydrostatic conditions or on rapid timescales can lead to PIA of the same
substance 6, 7 . The characteristic sensitivity to local vs longer-range structural order of the probe
technique used to investigate the phenomenon must also be taken into account in diagnosing
PIA events [Machon PMS].
In this notes, thermodynamics and kinetics of pressure-induced phase transitions will be
introduced before presenting two classical scenarios explaining PIA. Then, the concept of
configurational energy landscapes will be briefly discussed as it is a useful framework to interpret
relationships between crystalline and amorphous states. Classical examples of PIA will be used as
illustrations of the models introduced earlier. Finally, an emerging phenomenon, size-dependent
pressure-induced amorphization, will be introduced.
Pressure-induced phase transitions: thermodynamics vs kinetics
In the classical thermodynamics approach, the stable phase is given by the Gibbs-Duhem
stability criterion that implies, when one work with Pressure and Temperature as state variables,
that the stable phase must have the lower Gibbs energy. As the Gibbs energy is described by
=
dGm Vm dP S m dT (m: molar), the effect of pressure on this energy at constant
temperature is depicted on figure 1 for different phases. The stable phase (the one that must be
observed experimentally) has the lowest Gibss energy at given pressure and temperature.
Considering only the pressure effect, the Gibbs energy increases with pressure proportionally to
the molar volume. Therefore, the Gibbs energy of a given stable phase (phase 1 for instance) may
crossed the Gibbs energy of a denser phase (smaller molar volume) leading to a switch of the
phase which has the lowest energy.
Figure 1. (up) Gibbs energy as a function of pressure at ambient temperature T1 for three different hypothetical phases (i
= 1,3). The slopes of these energies are given by the molar volume of each phase. The stable phase is given by the lowest
Gibb energy. When the lines cross, the stable phase changes and a pressure-phase transition occurs (to a denser phase).
(bottom) Associated phase diagram in the (T, P) space.
226
The thermodynamics picture may be modified by the kinetics of the phase transition that is
governed by the energetic barrier between phase 1 and phase 2 (Figure 2). This barrier is related
to the atomic displacements needed for changing the coordination number and the symmetry of
the phase. Therefore, even though phase 2 should be observed experimentally, the transition
may be inhibited and phase 1 can be super-pressed in a metastable regime. The predicted
transition may then occur at any pressure depending on the experimental conditions (heating,
non-hydrostaticity, etc.).
The effect of kinetics is amplified at high pressure where the interatomic potential barriers are
important. However, this is also a classical effect observed in the cases of freezing or liquefaction
of gases. The possibility to superpress a low-pressure phase is at the core of the pressure-induced
amorphization phenomenon.
Figure 2. Thermodynamics vs kinetics in the case of a pressure-induced phase transition. At pressure below Pc, Phase 1
is the stable one. Above this critical pressure, phase 2 becomes stable. However, because of the energetic barrier the
transition may not occur. Phase 1 exists as a metastable state.
Pressure-induced amorphization: two classical scenarios

Cold melting
This first scenario has been inspired by Mishima who confirmed it experimentally by
pressurizing ice at low temperature (77K). As ice Ih had a negative (dTm/dP) melting slope that
could be extended metastably below its melting line (Fig. 3). This led to the prediction that low T
compression of the crystal might result in a cold melting event, as the glassy equivalent of the
liquid became equal in free energy to the metastably compressed crystal.
227
Figure 3. Schematic P-T construction depicting PIA as a metastable melting event. A low pressure crystalline phase (LP)
exhibits a negative initial Tm(P) melting slope and transforms via a first order transition to a denser (HP) polymorph at
high pressure (P1). The LP melting relation can be extended metastably to below the glass transition temperature (Tg). If
the LP crystal is compressed at a temperature sufficiently low to impede crystalline transitions its free energy relation will
intersect that of the metastable liquid or glassy state and PIA will occur (P2).
Mechanical instability
The cold melting scenario may apply to materials that have a melting line with dTm
dP
<0
either at ambient pressure or at high-pressure in the case of liquid-liquid phase transitions4.

If this not the case, another scenario may be invoked to understand the PIA and it is related to
the kinetics effect described in first section. The super-pressed LP phase may transform at any
pressure to a lower energy state but not necessary to the lowest energy state. Therefore, the
super-pressed LP phase can transform to an intermediate state that may be amorphous (Figure
4).
The LP phase must transform at some pressure as it cannot overcome its spinodal limit. A phase
can exist in a stable or metastable state but not in an unstable state. Under pressure, the
G
< 0 (meaning that the isothermal bulk modulus should be
P T
condition for stability is
positive). Reaching this limit, the kinetics barriers vanished and the system transforms to a lower
energy state. From this condition, one can derived stability criteria based on the elastic constant
of a crystalline state. These are known as Born criteria 8 . For example, for a three-dimensional
cubic solid the stability conditions can be expressed in terms of the elastic constants as
C11 + C12 > 0 ; C 44 > 0 ; C11 C12 > 0 .
228
Figure 4. An alternative view of the PIA event in terms of metastable free energy G(P) relations. The LP crystalline phase
is compressed metastably at low temperature beyond its first order transition point (P1). Its metastable G(P) curve cannot
continue indefinitely but must terminate at some critical value, shown as a point. The metastably extended LP phase may
also leave the G(P) curve below this value to seek the more stable surface of the HP phase. However if there is insufficient
thermal energy the system becomes trapped in a locus of amorphous states (shown shaded gray) and PIA has occurred.
Likewise, decompression-induced amorphization may occur as a HP phase is recovered metastably to ambient pressure
conditions (second shaded area above LP curve).
Configurational Energy Landscapes
A convenient framework for interpreting the complex phenomenology surrounding PIA as well
as polyamorphism is provided by configurational energy landscape (CEL) models 9 .These are
constituted by a multi-dimensional plot of the potential energy (E) developed for all possible
interparticle arrangements, defined by the bonding or other short- vs long-range interactions
between them. Each atomic arrangement constitutes a configuration that is typically
represented schematically as a plot of E vs one or more of the generalized configurational
coordinates. Between the deep, sharp minima representing ordered crystalline materials in the
CEL occurs a landscape of amorphous configurations. As the pressure is varied, parts of the
CEL change with respect to barrier heights, relative positions of minima and pathways between
these that can be explored by thermal excitation, resulting in the variation of phase transition
temperatures including melting, and the observation of metastable events such as PIA, or
polyamorphism. The CEL is affected by pressure vs non-hydrostatic stress fields including shear
forces in different ways and thus drive transformations that result in stabilization of new
crystalline or amorphous polymorphs.
Two main scenarios are envisaged (Figure 5). In the first, the overall form of the CEL is assumed
to remain unchanged as the pressure increases, although the relative depth of potential minima
and the barriers between them vary according to the relative density stabilization of different
structural states. Pressurization at low temperature allows the crystal to be compressed
metastably beyond its normal stability limit, until the P.V contribution to the energy allows the
system to overcome local barriers and thus sample the surrounding configurational states.
However, the thermal energy in the system is not sufficient to allow nucleation and growth of a
suitable crystalline phase and the resulting material is amorphous. In a second scenario, the
229
topology of the CEL becomes modified during pressurization with the appearance,
disappearance or other modification of various minima and the barriers between them caused by
mechanical, vibrational or electronic instabilities leading to collapse of the crystalline structure,
but once more without permitting growth of a new crystalline phase.
Two critical factors govern the amorphization process: (i) the depth of the energy minima
representing different crystalline states; (ii) the height of the energy barrier with respect to the
amorphous megabasin, which can be increased by the number of defects (induced by doping,
irradiation, etc.), surface/interface energy, strain, etc. Whenever this increase is sufficiently high,
the initial crystal structure may be destabilized in favor of a new, non-crystalline atomic
configuration. Since the energy barrier between two crystalline phases that undergo
reconstructive phase transformation is higher due to the need for bond breaking and atomic
diffusion events, amorphization may be easier to achieve under the low temperature and finite
timescale conditions of the experiment.
Figure 5. Two main scenarios for the pressure effects on the CEL: (left) the CEL is not modified by the pressure but the
potential energy of a crystal C1 is increased by an amount of elastic energy P.V. Depending on the energy barrier, this
crystal can transform to the thermodynamic stable crystal C2 or to a metastable amorphous state. Note that the energy
increase may be also due to other processes: irradiation, surface/interface, chemical, etc. that may also lead to an
amorphization; (right) the CEL itself becomes modified during pressurization resulting in the appearance of instabilities
leading to collapse of the crystal structure towards an amorphous state.
Classical example of PIA

Ice Ih
During compression of ice Ih at 77 K a rapid reduction in molar volume was observed to occur at
approximately 1.1 GPa and the solid material recovered at ambient pressure was found to be
amorphous upon X-ray examination. It was concluded that PIA had occurred, at a pressure that
corresponded approximately to the predicted crossing of the free energy curves of the
metastably compressed crystal and the solidified glassy state. That observation and its
interpretation have resulted in the emergence of a new research field linking crystalline, glassy
and liquid state physics.
Mishimas initial experiments led to discussions about the PIA mechanism, and if it could be
considered as a conventional two-phase melting event extended metastably to a temperature
well below the glass transition (Tg), or instead related to one phase or mechanical instability230
related melting phenomenon. The leading idea of Mishima inspired by Kawais works 10 was
related to the negative slope melting line of ice. The seminal experiment was designed to test the
effect of compressing ice cooled to low temperature (<150 K), to intersect the metastable
extension of the melting curve extended to high pressure below the melting curve [Mishima]
(Figure 3). However, an alternative interpretation of the ice Ih-to-amorphous transition suggests
that the amorphous state is formed by mechanical collapse of ice Ih when it is metastably
compressed 11, 12 . This second mechanism envisaged the PIA event as due to collapse of the
crystal due to an elastic instability. MD simulations have supported this scenario by
demonstrating rapid decrease of the elastic constants C11, C12, C13 and C33 as a function of
pressure [Tse J Phys chem].
Mishima included both possible mechanisms in a more general interpretation of ice PIA
showing that in a first region of the phase diagram, the metastable melting mechanism could
apply, while at higher pressures elastic instabilities become the main factor leading to the
amorphous state 13 . Lattice dynamics calculations confirming the existence of such a crossover at
160 K [tse nature], that has also been confirmed by experimental measurements of the phonon
density of states 14 .
SiO2
Shortly after the report of PIA for ice Ih, R. Hemley et al reported a similar effect occurring for
the SiO2 minerals -quartz and coesite 15 . These phases are structurally related to ice polymorphs
with SiOSi bridges between tetrahedral SiO4 units taking the place of H-bonded H2O
frameworks. Using in situ X-ray diffraction in a diamond anvil cell they showed that the
crystalline materials transformed into amorphous solids at between 25-35 GPa at ambient
temperature and developed a similar interpretation to Mishima et al. in terms of a metastable
"melting" event. Although neither quartz nor coesite exhibit a negative melting relation, the
authors proposed that a maximum might appear in Tm(P) for both phases in the 0-10 GPa
region, permitting the argument of incipient crossing of the metastably compressed crystalline
and glassy free energies below Tg. Later work proposed alternative interpretations of the SiO2
amorphization event in terms of a crystalline mechanical instability, similar to that suggested for
H2O ice Ih 16 . However, careful compression of single crystalline quartz under quasi-hydrostatic
conditions resulted in transformation into a metastable crystalline (quartz-II) phase rather than
PIA [kingma]. It was also found that PIA can be suppressed completely using He as a highly
hydrostatic PTM, and a monoclinic structure was found when decompressed from 45 GPa 17 .
Very recently, based on molecular dynamic simulations, it has been shown that this rich
phenomenology can be rationalized through a unified theoretical framework of the atomistic
pathways leading to densification 18 . This model emphasizes the role played by the oxygen
sublattice, which transforms from a bcc-like order in quartz into close-packed arrangements in
the denser structures, through a ferroelastic instability of martensitic nature in accordance with
the ferroelastic glass model 19 .
231
PIA of nanocrystalline materials

In nanoparticles, the surface considered as an extended defect is associated with a positive excess
entropy, that is augmented by the presence of surface defects. The presence of point defects
within nanoparticles leads to stabilization of the liquid or a solid amorphous phase and the
thermodynamics and kinetics of melting or PIA transitions are affected.
Recently, size-dependent pressure-induced amorphization effects have been reported. Below a
critical diameter, an amorphous state is observed to form under pressure instead of the expected
high pressure polymorph. For instance, it has been shown that for particle diameters below 10
nm, TiO2 nanoparticles undergo a PIA event. Such size dependent pressure- induced
amorphization has also been reported for Y2O3 nanoparticles 20 . When the particles diameter is
above 21 nm, the initial cubic structure exhibits a transition to a hexagonal structure phase at 14
GPa. A different scenario is observed for particles with a diameter of 16 nm for which the cubic
phase transforms to an amorphous state at 25 GPa.
From these results nanoparticles of TiO2 and Y2O3 undergo PIA when a critical diameter of the
particles is reached. However, it has been recently shown that reduced particle size is not
sufficient in order to explain the amorphization process. In TiO2, the possible high-pressure
transformations (crystalline baddeleyite vs amorphous) in nanoparticles with d < 10 nm depend
also on the degree of surface functionalization 21 . Such an effect has also been shown to occur for
Y2O3 22 . Adsorbed molecules at the surface can impede recrystallization and induce disorder
leading the transition pathway to an amorphous state at high-pressure. All these considerations
have been included in a model based on a thermodynamic and geometric approach based on the
Ginzburg-Landau theory of phase transitions and percolation approach 23 .
Conclusions
The occurrence of PIA has raised fundamental questions about metastability and phase
relationships in systems compressed or decompressed at low temperature. As a system is
perturbed from its initial equilibrium state any transition between stable phases associated with
processes that involve energetic barriers or species diffusion becomes kinetically hindered and
the system can find itself trapped in a locus of structurally disordered metastable states. If the
system is initially in a non-equilibrium amorphous state it can be induced to cross a barrier into
another basin of amorphous states with different density through the application of pressure,
resulting in pressure-induced polyamorphism. Sampling of deep crystalline minima may also
occur simultaneously with the PIA or polyamorphism phenomena, leading to technologically
useful strategies for formation of novel nanocomposite materials containing intimate mixtures of
crystalline and amorphous regions or inclusions.
232

References
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making amorphous solids, Nature 310: 393-5.
2 Machon, D., Meersman, F., Wilding, M.C., Wilson, M., and McMillan, P.F., 2014, Pressure-induced
amorphization and polyamorphism: inorganic and biochemical systems, Progr. Mater. Sci. 61: 216-282.
3 Ponyatovsky, E.G., and Barkalov, O.I., 1992, Pressure-induced amorphous phase,. Mater. Sci. Rep. 8: 147-91.
4 Sharma, S.M., and Sikka, S.K., 1996, Pressure induced amorphization of materials, Progr. Mater. Sci. 40: 1-77.
5 Richet, P., and Gillet, P., 1997, Pressure-induced amorphization of minerals: a review, Eur. J. Mineral. 9: 907-933.
6 Kingma, K.J., Hemley, R.J., Mao, H.-k., and Veblen, D.R., 1993, New high-pressure transformation in quartz, Phys. Rev. Lett., 70: 3927-30.
7 Ekbundit, S., Leinenweber, K., Yarger, J.L., Robinson, J.S., Verhelst-Voorhees, M., and Wolf, G.H., 1996, New highpressure phase and pressure-induced amorphization of Ca(OH)2: grain size effect, J. Solid State Chem. 126: 300-7.
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9 Wales, D.J., 2003, Energy Landscapes, Cambridge, UK, New York: Cambridge University Press.
10 Mishima, O., 2013, Polyamorphism in Water, Adv. Chem. Phys. 152: 355.
11 Tse, J.S., 1992, Mechanical instability in ice Ih. A mechanism for pressure induced amorphization, J.
Chem. Phys. 96: 5482.
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for pressure-induced amorphization of ice Ih, Nature 400:647.
13 Mishima, O., 1996, Relationship between melting and amorphization of ice, Nature 384: 546.
14 Strassle, T., Klotz, S., Hamel, G., Koza, M.M., and Schober, H., 2007, Experimental Evidence for a Crossover
between Two Distinct Mechanisms of Amorphization in Ice Ih under Pressure, Phys. Rev. Lett. 99: 175501.
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amorphization of crystalline silica, Nature, 334: 52-4.
16 Binggelli, N., and Chelikowsky, J.R., 1992, Elastic instability in alpha-quartz under pressure, Phys. Rev.
Lett. 69: 2220.
17 Haines, J., Leger, J.M., Gorelli, F., and Hanfland, M., 2001, Crystalline Post-Quartz Phase in Silica at
High Pressure, Phys. Rev. Lett. 87:155503.
18 Liang, Y., Miranda, C.R., and Scandolo, S., 2015, Atomistic pathways of the pressure-induced
densification of quartz, Phys. Rev. B 92: 134102.
19 Toldano, P., and Machon, D., 2005, Structural mechanism leading to a ferroelastic glass state:
Interpretation of amorphization under pressure, Phys. Rev. B 71: 024110.
20 Wang, L., Yang, W., Ding, Y., Ren, Y., Xiao, S., Liu, B., et al., 2010, Size-Dependent Amorphization of
Nanoscale Y2O3 at High Pressure, Phys. Rev. Lett. 105: 095701.
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233
High-pressure crystallization
Andrzej Katrusiak, Faculty

of Chemistry,
Adam Mickiewicz University, Pozna,
High-pressure
crystallization
URL: hpc.amu.edu.pl
Andrzej Katrusiak
Dedicated to the memory of Prof. Lodovico Riva di Sanseverino (1939 - 2010)
Faculty of Chemistry, Adam Mickiewicz University, Pozna, Poland

katran@amu.edu.pl
www.hpc.amu.edu.pl
Dedicated to the memory of Prof. Lodovico Riva di Sanseverino (1939 - 2010)
Introduction
Most of crystals in industry and in scientific laboratories are made at ambient pressure. This
equally concerns steel, other metals and pharmaceutical ingredients, but also bio-crystals formed
in the living tissues. At the same time we are aware that the conditions on the surface of Earth
are unique in the Universe and that solid materials formed in the interstellar space or inside
planets are exposed to the pressure either lower or higher than that of the atmosphere of Earth.
One of the best known examples is diamond. Its formation requires the pressure of several GPa,
high temperature and access of oxygen sealed off, which takes place in the deep geological
deposits of carbon. Hence for centuries diamond could be mined only, except for the sites where
the tectonic movements brought the deeper ledges to the surface. Nonetheless, diamond
exemplifies the exceptional qualities that can be achieved by using the pressure for
crystallizations. For this reason the high pressure crystallization of carbon was intensely
investigated and in the 1950's the successful crystallization of diamond in laboratory was
announced. Despite some opposition from the mining industry, the production of 'artificial'
diamonds developed quickly and before the end of 20th century the production of 'artificial'
diamonds exceeded the amounts of 'natural' mined diamonds. Today it would be difficult to
satisfy the demands of industry for this hardest material and the best heat conductor by natural
diamonds only. On the other hand, the high-pressure crystallization is still quite 'exotic' and it is
mainly considered only in scientific laboratories for obtaining new materials. Of course one can
ask if the high-pressure crystallization is really needed (for other purposes than the production
of diamonds, which are generally in demand). Another question is if w can predict properties of
materials crystallized at high pressure. Some people believe that there are materials harder than
diamond and that they can be obtained at high-pressure conditions only. Naturally, hardness is
not the only property required for special materials. Just the opposite is often needed for
example softer and more soluble forms of compounds are required for pharmaceutical
applications. Is it possible to generally predict the properties of materials obtained from highpressure crystallizations? Presumably yes, although such rules are still to be formulated and the
most reliable method is the experimental verification of predictions. In this lecture several
compounds have been selected to illustrate various aspects of high-pressure crystallizations and
their products.
234
Several rules of high-pressure crystallization can be formulated basing on the thermodynamic

information. The methods and experiments chosen for this chapter are mainly limited to the
high-pressure crystallization of organic compounds, and a huge methodology optimized for
inorganic compounds and super-hard materials has been intentionally excluded.
Last, but not the least, the high-pressure crystallization can be employed for obtaining good
quality crystals of compounds in the same form as the ambient-pressure phase. There are
compounds, for which no good quality crystals could be obtained at normal conditions, for
example by diffusion, evaporation of the solution or by lowering temperature. However, the
crystallization in high pressure yielded beautiful crystals, for which their structure could be easily
determined. In other cases, the determination of molecular dimensions of a compound was
hampered by strong disorder of molecules at ambient pressure, whereas in the high-pressure
phase he molecules were ordered and high-accuracy structural dimensions were determined.
Single crystals of some high-pressure phases, when obtained by compression of the lowerpressure phases, can break into small pieces which hampers the single-crystal determination of
their structure. These difficulties can be circumvented by the in-situ crystallization in the
pressure region of the investigated phase. The examples of these different applications of highpressure crystallization will be given.
High-pressure crystallization using a DAC
Usually, crystallizations in isobaric conditions, at atmospheric pressure at 0.1 MPa, are
performed by increasing the concentration of the solution (by evaporating the solvent or by
decreasing the temperature), by freezing the melt, by sublimation, and by very many other
techniques that will not be discussed here. Like other techniques, the high-pressure
crystallization requires a precise control of the thermodynamic parameters. One of advantages of
high-pressure crystallization in a diamond-anvil cell (DAC) is that it proceeds relatively quickly,
and one can visually monitor the progress of the crystal growth and adjust the conditions when
required.
The high pressure crystallization of a compound can be planned on its p-T phase diagram,
like a trip route is planned on a map. High pressure crystallization is particularly suited for the
compounds liquid at normal conditions. For example, the phase diagram of 1,1,2trichloroethane (TCE, C2H3Cl3), liquid at normal conditions and freezing at 237 K at 0.1 MPa
into solid phase I, is shown in Figure 1. Such a crystallization process by lowering temperature at
0.1 MPa is describes as isobaric crystallization. Alternatively, the region of solid phase I of TCE
can be entered at room temperature by increasing pressure to 0.38 GPa.
235
Figure 1. Left: p-T phase diagram of 1,1,2-trichloroethane, including the gas (yellow), liquid (white) and two solid phases
(blue and red), but excluding the region below 0.1 MPa (i.e. 0.0001 GPa); RT denotes the room temperature, which leaves
the triple point and the sublimation curve outside the plotted region; Right: a single crystal of 1,1,2-trichloroethane
grown in isochoric conditions in a DAC.
When the pressure is slowly increased at room temperature, the crystallization proceeds in
isothermal conditions.
Transitions to the solid phase II destroy single crystals, which hampers the determination of its
structure. Therefore TCE was crystallized in situ in phase II at the conditions of its stability.
Initially, the pressure was increased to about 0.5 GPa, and then temperature was increased till all
the sample, except one small seed melted. Then temperature was slowly decreased to 295 K, and
the single crystal grew, as shown in Figure 1. This crystallization, when pressure adjusts to the
varied temperature and the volume of the DAC chamber is fixed, is described as isochoric
crystallization. The subsequent determination of the crystal structure revealed a transformation
between conformers gauche and transoid in phases I and II, respectively [A1].
Another example of a high-pressure crystallization will be described for urea. In 1916, Bridgman
phase II of urea above 373 K and 0.60 GPa, phase III at 293 K above 0.48 GPa [A2]. Another
solid-solid phase transition of urea takes place at 2.8 GPa. The transition from phase I to phase II
is destructive and the determination of phases II and III required recrystallization of the sample
at isochoric conditions, as illustrated in Figure 2. Urea is solid at normal conditions, and in order
to facilitate the crystallization we added some solvent. Thus in contrast to TCE, that was
crystallized by freezing the melt of the neat compound, the crystallizations of urea phases I, III
and IV were performed of the aqueous solution phases I and III) and of the solution in
methanol:ethanol:water (16:3:1 vol.) mixture (phase IV). The high-pressure structures of phases
I, III and IV of urea were determined as an undergraduate project by Kinga Ostrowska
supervised by Dr. Anna Olejniczak [3]
236
Figure 2. Single crystals of urea phases I (left), III (centre) and IV (right) grown in situ in the diamond-anvil cell chamber
in isochoric conditions. Miller indices of crystal faces are given in rounded brackets.
Thermodynamic background
High-pressure crystallization can be generally described in a p-T phase diagram, shown in Figure
3. When the thermodynamic conditions are changed from liquid to the solid region, the crystals
usually nucleate (unless the melt/solution is super-cooled or over-pressurized). Within the solid
region, a proximity to the melting curve is favourable for larger grains and for growing single
crystals. Further distance to the melting curve causes quicker nucleation of many seeds. If the
conditions are changed very quickly to the temperature too low, or pressure too high, the
substance can form an amorphous state. This process is called vitrification, and the regions of
nucleation and vitrification are separated by the vitrification curve.
Figure 3. Schematic p-T phase diagram of a pristine compound (left) and of its mixture with a solvent (right).
The phase diagram in Figure 3 illustrates the situation with two solid phases I and II. The
crystallization from the melt (left diagram) leads to the crystals of phase I, and when the phase
transition between phases I and II is destructive, no good quality single crystals of phase II can be
obtained. However, by dissolving the compound, the dissolution curve can be moved toward the
solid phase II (Figure 3). Consequently, the crystallization can be perform in situ in the region of
phase II and a single crystal of phase II can be grown in this way. This method of accessing highpressure phases of urea was applied.
The advantages of using the solvent for high-pressure crystallization are apparent from the
binary-system diagrams shown in Figure 4. They plot the phases of two mixed compounds as a
function of concentration, temperature and pressure. A typical mixture of a substance (denoted
237
B) solid at normal conditions and a solvent (compound A) has been schematically depicted in
these diagrams. The increased concentration of the solvent decreases the temperature of
precipitation of compound B. As the parameter of pressure is concerned, in most cases it acts
opposite to the effect of temperature. In fact, a rule of reverse effects of temperature and pressure
effects was formulated and there are few exceptions from this rule [4]. So the increased
concentration of the solvent (compound A) increases the pressure of precipitation. This effect
can be employed for accessing a new solid phase of compound B: in Figure 4 the 50-50
concentration of compounds A and B allows the direct crystallization of compound B in its
phase II at about 0.35 GPa.
Figure 4. Schematic binary diagrams of compounds A and B as a function of temperature (left) and pressure (right).
Please note the reverse sense of the temperature axis (upward) and the pressure axis (downward).
It can happen, that the polymorphs obtained at high pressure can be recovered to ambient
conditions. Moreover, they can be also used for seeding the crystallizations at normal conditions
and in this way high-pressure polymorphs can be produced at normal conditions [5].
Hidden polymorphs
The p-T phase diagrams of substances often contain phases, which do not form easily when the
substance is compressed only. Thus there are phases, which require an in situ recrystallization in
the conditions of stability of the phase. This becomes quite a common feature, which has been
evidenced for several substances. In other words, when a compound in its ambient-pressure phase
is compressed, it can remain in phase I despite being less stable (i.e. metastable) than another
phase II. For example, imidazole (C3H4N2) phase I can be compressed to 3 GPa at least, but its
recrystallization at 1.2 GPa yields a new phase II. Imidazole phases I and II are very different:
phase I is centrosymmetric (space group P21/c), while phase II is polar (space group Aba2).
However both these phases I and II are built of the molecules NHN bonded into chains [6].
High-pressure solvates/ansolvates
Many substances change their preference of crystallizing as a neat compound or a solvate

depending on the thermodynamic conditions, and high pressure can be used for finding new
238
forms of compounds [7]. In this way the only hydrates of thiourea were obtained recently [8].
Usually the molecular volume (calculated as the unit-cell volume divided by Z) of the solvated
crystal is larger than that of the neat compound. However we have evidenced a reverse case,
when the hydrated crystal is smaller than the neat compound of 5,6-dimethylbenzymidazole [9].
Moreover, this hemihydrate has been kept in on open vial for several years in our laboratory, and
no signs of deterioration have been noticed in the crystals.
High-pressure reactions
High pressure can also trigger chemical reactions, for example of N-methylation, polymerization
and disproportionation of salts [10]. Examples of such reactions will be given.
Conclusions
Undoubtedly, the high-pressure crystallization facilitates the high-pressure research and offers
new possibilities in the materials chemistry and science. This chapter is too short for fully
describe this subject, but numerous publication are available, as exemplified by the selection of
papers in the list of references below [11-31]
References
[1] M. Bujak, M. Podsiado, A. Katrusiak, Energetics of conformational conversion between 1,1,2trichloroethane polymorphs, Chem. Commun. (2008) 44394441.
[2] Bridgman, P. W. Proc. Am. Acad. Arts Sci. 1916, 52, 91187
[3] A. Olejniczak, K. Ostrowska, A. Katrusiak, H-Bond Breaking in High-Pressure Urea, J. Phys. Chem. C 113
(2009) 15761-15767.
[4] W. Cai, A. Katrusiak, Giant negative linear compression positively coupled to massive thermal
expansion in a metal-organic framework, Nature Commun, 5 (2014) Article number: 4337.
[5] F.P.A. Fabbiani, D.C. Levendis, G. Buth, W.F. Kuhs, N. Shankland, H. Sowa Searching for novel crystal
forms by in situ high-pressure crystallisation: the example of gabapentin heptahydrate, CrystEngComm,
2010, 12, 2354-2360.
[6] D. Paliwoda, K. F. Dziubek, A. Katrusiak, Imidazole Hidden Polar Phase, Cryst. Growth Des. 12 (2012)
43024305.
[7] A. Olejniczak, A. Katrusiak, Pressure-Induced Hydration of 1,4-Diazabicyclo[2.2.2]octane Hydroiodide
(dabcoHI), Cryst. Growth Des. 11 (2011) 22502256.
[8] H. Tomkowiak, A. Olejniczak, A. Katrusiak, Pressure-Dependent Formation and Decomposition of
Thiourea Hydrates, Cryst. Growth Des. 13 (2013) 121125.
[9] W. Zieliski, A. Katrusiak, Hydrate smaller than the anhydrate, CrystEngComm 17 (2015) 54685473.
[10] A. Olejniczak, A. Katrusiak, Pressure induced transformations of 1,4-diazabicyclo[2.2.2]octane (dabco)
hydroiodide: diprotonation of dabco, its N-methylation and co-crystallization with methanol,
CrystEngComm, 12 (2010) 25282532.
[11] F.P.A. Fabbiani, B. Dittrich, A.J. Florence, T. Gelbrich, M.B. Hursthouse, W.F. Kuhs, N. Shankland, H.
Sowa, Crystal structures with a challenge: high-pressure crystallisation of ciprofloxacin sodium salts and
their recovery to ambient pressure, CrystEngComm, 2009, 11, 1396-1406
239
[12] F.P.A. Fabbiani, D.R. Allan, S. Parsons, C.R. Pulham, Exploration of the high-pressure behaviour of
polycyclic aromatic hydrocarbons: naphthalene, phenanthrene and pyrene, Acta Cryst. B 2006, 62,826-842.
[13] I.D.H. Oswald, I. Chataigner, S. Elphick, F.P.A. Fabbiani, A.R. Lennie, J.Maddaluno, W.G. Marshall, T.J.
Prior, C.R. Pulham, R.I. Smith, Putting pressure on elusive polymorphs and solvates, CrystEngComm, 2009,
11, 359-366.
[14] E.V. Boldyreva, High-pressure diffraction studies of molecular organic solids. A personal view, Acta
Cryst. (2008). A64, 218-231
[15] E.V. Boldyreva, Multicomponent organic crystals at high pressure, Z. Kristallogr. 2014,
229, 236-245
[16] R. Lee, J.A.K. Howard, M.R. Probert, J.W. Steed, Structure of organic solids at low temperature and
high pressure, Chem. Soc. Rev. 2014, 43, 4300-4311
[17] F.P.A. Fabbiani, D.R. Allan, W.I.F. David, A.J. Davidson, A.R. Lennie, S. Parsons, C.R. Pulham, J.E.
Warren, High-Pressure Studies of Pharmaceuticals: An Exploration of the Behavior of Piracetam, Cryst.
Growth Des. 2007, 7, 1115-1124.
[18] D.R. Allan, S.J. Clark, A. Dawson, P.A. McGregor, S. Parsons, Pressure-induced polymorphism in
phenol, Acta Cryst. B 2002, 58, 1018-1024
[19] D.R. Allan, S.J. Clark, M.J.P. Brugmans, G.J. Ackland, W.L. Vos, Structure of crystalline methanol at
high pressure, Phys. Rev. B 1998, 58, R11809-R11812
[20] D.R. Allan, S.J. Clark, Comparison of the high-pressure and low-temperature structures of ethanol and
acetic acid, Phys. Rev. B 1999, 60, 6328-6334
[21] D.R. Allan, S.J. Clark, Impeded dimer formation in the high-pressure crystal structure of formic acid,
Phys. Rev. Lett. 1999, 82, 3464-3467
[22] R.M Ibberson, S. Parsons, D.R. Allan, A.M.T. Bell, Polymorphism in cyclohexanol, Acta Cryst. B 2008,
64, 573-582.
[23] P.A. McGregor, D.R. Allan, S. Parsons, S.J.Clark, Hexamer formation in tertiary butyl alcohol (2methyl-2-propanol, C4H10O), Acta Cryst. B 2006, 62, 599-605.
[24] J. Ridout, M.R. Probert, High-pressure and low-temperature polymorphism in C-HF-C hydrogen
bonded monofluorotoluenes, Cryst. Growth Des. 2013, 13, 1943-1948.
[25] J. Ridout, M.R. Probert, Low-temperature and high-pressure polymorphs of isopropyl alcohol,
CrystEngComm 2014, 16 (32), pp. 7397-7400
[26] P. Loubeyre, M. J.-L., Letoullec, R. Charon-Grard, High pressure measurements of the He-Ne binary
phase diagram at 296 K: Evidence for the stability of a stoichiometric Ne(He)2 solid, Phys. Rev. Lett. 1993,
70, 178-181.
[27] S. Block, C.E. Weir, G.J. Piermarini, High-Pressure Single-Crystal Studies of Ice VI. Science 1965, 148,
947948
[28] A.van Valkenburg, Visual Observations of High Pressure Transitions, Rev. Sci. Instrum. 1962, 33, 1462.
[29] A.van Valkenburg, H.-K. Mao, P.M. Bell, Carnegie Inst. Washington Yearb. 1971, 70, 237238.
[30] A. Olejniczak, A. Katrusiak, M. Szafraski, Ten Polymorphs of NH+N Hydrogen-Bonded 1,4Diazabicyclo[2.2.2]octane Complexes: Supramolecular Origin of Giant Anisotropic Dielectric Response in
Polymorph V, Cryst. Growth Des. 10 (2010) 35373546.
[31] A. Katrusiak, M. Szafraski, M. Podsiado, Pressure-induced collapse of guanidinium nitrate NHO

bonded honeycomb layers into a 3-D pattern with varied H-acceptor capacity, Chem. Commun. 47 (2011)
21072109.
240
Crystal structure prediction and metadynamics simulations at high pressure
CrystalMartok,
structureDepartment
predictionofand
metadynamics
at
Roman
Experimental
Physics,simulations
Comenius University
in Bratislava,
high pressure
Mlynsk
dolina F2, 842 48 Bratislava, Slovakia
email: martonak@fmph.uniba.sk
Roman Martok
Dept of Experimental Physics, Comenius Univ. in Bratislava, Bratislava, Slovakia

martonak@fmph.uniba.sk
Abstract
We present here the basic ideas of the metadynamics-based approach to simulation of structural
transformations in crystals. The technique is illustrated on the example of pressure-induced
polymerization of molecular nitrogen crystal.
Keywords
computer simulations, structural transformations, metadynamics
Introduction
Structure is a key property of condensed matter system, determining all of its physical
properties. Crystal structure prediction and study of structural transformations in crystals are
therefore of importance both for our fundamental understanding of solids and for practical
applications. In past decades we have seen remarkable progress on the experimental side where
pressures in the Mbar range can now be reached routinely and time-resolved information can be
obtained. More recently, in past two decades or so, dramatic progress has been reached also on
the theory side and the solution of the crystal structure prediction problem for systems with
moderate complexity has become a routine task due to number of optimization algorithms, such
as direct search[1], evolutionary algorithms[2], particle swarm optimization [3], etc.
Perhaps surprisingly in this context, realistic study of structural transformations in solids by
dynamical computer simulations still represents a challenge. The motivation for such study is
clear - it would directly reveal the microscopic transition mechanism and allow to understand
the kinetics. This would be highly valuable e.g. for synthesis of new materials. The first
milestone in this field was the introduction of the variable-cell molecular dynamics scheme by
Parrinello and Rahman [4] which for the first time allowed a direct study of structural
transformations in crystals at constant-pressure conditions. It became soon clear, however, that
the approach suffers from the well-known time-scale problem common to all activated
processes. Structural transformation in dense condensed matter system often involves crossing
of substantial free-energy barrier between the initial and final free-energy well. Even in
experiment first-order reconstructive transitions are typically sluggish and take place on long
time scales ranging to hours and more. At the same time pronounced hysteresis is often found
and in order to observe e.g. a pressure-induced transformation it might be necessary to
overpressurize the system. Clearly, plain MD providing access to time scales ranging from ps or
241
at most ns in case of ab-initio MD to s in case of classical force-fields is not well-suited to study

this kind of activated processes. In order to observe the transition within the available simulation
time scale the overpressurization has to be much stronger than in experiment and as a result one
is often forced to apply pressure which is order of magnitude higher than the thermodynamic
one. In such case it is doubtful to what extent the simulation represents the real process at
equilibrium conditions the microscopic mechanism is likely to be substantially different and
one or more phases in the phase diagram may be even skipped. The problem clearly originates
from the inefficiency of standard MD in simulation of activated processes when the barrier is
substantially larger than the thermal energy and barrier crossing is a rare event.
Here we briefly present one of possible approaches towards simulations of structural phase
transitions in crystals, based on the generic metadynamics algorithm by Laio and Parrinello[5].
We start by a short description of the generic algorithm. The problem of crossing the barrier in a
system consisting of N atoms involves 3N degrees of freedom which is usually a large number
and makes the problem complicated. The metadynamics approach is based on substantial
reduction of this number by means of employing a suitably chosen low-dimensional order
parameter h which is able to distinguish between the initial and the final state of the system. The
main idea is to iteratively construct a biasing potential able to help the system to cross the
barrier. This is performed by means of a discrete steepest-descent-like dynamics in the order
parameter space with step h
which is driven by the gradient
of the modified free-energy Gt
This includes a history-dependent term keeping track of the region of the order parameter space
which has been previously visited by the dynamics, by means of placing a Gaussian with height
W and width h. As the discrete time goes on the system progressively explores the basin of
attraction of the initial equilibrium state and is gradually forced to visit configurations with
higher free energy. Upon reaching the top of the barrier the dynamics eventually enters into the
basin of attraction of another equilibrium state. The approach can be used e.g. to study chemical
reactions or first-order phase transitions provided a suitable order parameter can be identified.
242
An early application of this algorithm was the metadynamics-based technique for simulation of
structural phase transitions in crystals[6]. This approach borrowed from the Parrinello-Rahman
MD the idea of variable simulation supercell h=(a,b,c) which was used as order parameter able
to distinguish the original and final crystalline structure. Here, a,b,c are supercell vectors and h
is a 3x3 matrix. This matrix, however, includes also global rotation of the system which is
irrelevant for the structure. Therefore the rotation needs to be eliminated which can be
accomplished e.g. by requiring the h matrix to be upper triangular[7]. The derivative of the
Gibbs free energy with respect to the components of the h-matrix can be simply calculated [7]
from the averaged internal pressure tensor p as follows (P is the external hydrostatic pressure
and V is volume of the system)
We note that this basic version of the technique was further improved in Ref. [8] by employing
as order parameter suitably chosen rescaled linear combinations of the h matrix components.
This approach allows for more uniform sampling of the order parameter space without the need
for using very small Gaussian size.
The metadynamics simulation is practically performed by means of a series of standard
constant-volume NVT MD simulations (metasteps), with typical duration of the order of 1 ps.
Suitable system size is up to few hundred atoms which makes this kind of simulation feasible also
on ab initio level. Starting from the initial structure stronger and stronger deformations are
applied to the system until it crosses the barrier and enters into the basin of attraction of a new
structural phase [6-11].
The approach described has been applied to a number of systems, including e.g. benzene [12],
MgSiO3 [13], P [14], SiO2[15], Si [16], CO2 [17], C [18], Ca [19], CdSe [20], BI3 [21], BN [22], Sn
[23], B2X4 [24], Mg [25], Si [26], H [27], GaN [28], Ta [29], Ge [30], MoS2 [31], N2 [32], Xe [33].
etc. Most of these studies were performed by means of ab initio MD; we note that in Ref. [16]
neural network-based potential was employed instead.
As an example of the application of this approach we mention here the recent study of pressureinduced polymerization of molecular nitrogen crystal [32]. In this work the simulation started
from the Immm molecular phase and after a series of transitions (see Fig.1) reached the final
polymeric cg-N phase. The figure shows the evolution of enthalpy as well as relevant structures
at intermediate stages of the complex transformation.
243
Figure1. Evolution of enthalpy and structure during metadynamics simulation starting from the Immm molecular N2 at
110 GPa and 1500 K. From Ref.[32].
For more detailed information we refer the reader to literature. In Refs. [6,8] the methodology is
described, Refs.[7,9-11] are review papers and Refs. [12-33] are devoted to specific applications.
Acknowledgments
I acknowledge collaboration on metadynamics applications with S. Arapan, C. Bealing, J. Behler,
A. Belonoshko, M. Bernasconi, C. Ceriani, D. Donadio, L. Grajcarov, S. Jahn, D.D. Klug, O.
Kohulk, A. Laio, S. Leoni, C. Molteni, A.R. Oganov, M. Parrinello, S. Patchkovskii, D. Plaienka,
P. Raiteri, S. Scandolo, D. Selli, J. Sun, E. Tosatti, and Y. Yao (in alphabetical order). I also
acknowledge support by VEGA grant No. 1/0904/15.
References
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[2] A. Oganov and C. Glass, J. Chem. Phys. 124, 244704 (2006).
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[4] M. Parrinello and A. Rahman, Phys. Rev. Lett. 45, 1196 (1980).
[5] A. Laio and M. Parrinello, Proc. Natl. Acad. Sci. USA 99, 12562 (2002).
[6] R. Martok, A. Laio, and M. Parrinello, Phys. Rev. Lett. 90, 075503 (2003).
[7] R. Martok, A. Laio, M. Bernasconi, C. Ceriani, P. Raiteri, F. Zipoli, and M. Parrinello, Zeitschrift fr
Kristallographie 220, 489 (2005).
[8] R. Martok, D. Donadio, A. R. Oganov, and M. Parrinello, Nature Materials 5, 623 (2006).
[9] R. Martok, A. R. Oganov, and C. W. Glass, Phase Transitions 80, 277 (2007).
[10] R. Martok, Eur. Phys. J. B 79, 241 (2011).
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[12] P. Raiteri, R. Martok, M. Parrinello, Angewandte Chemie Int.Ed. 2005, 44, 3769.
[13] A. R. Oganov, R. Martok, A. Laio, P. Raiteri, M. Parrinello, Nature 438, 1142 (2005); S. Jahn, R.
Martok, Phys. Chem. Min. (2008) 35:1723.
[14] T. Ishikawa, H. Nagara, K. Kusakabe, N. Suzuki, Phys. Rev. Lett. 96, 095502 (2006).
[15] R. Martok, D. Donadio, A. R. Oganov, M. Parrinello, Nature Materials 5, 623 (2006); D. Donadio, R.
Martok, P. Raiteri, M. Parrinello PRL 100, 165502 (2008).
[16] J. Behler, R. Martok, D. Donadio, M. Parrinello, PRL 100, 185501 (2008).

[17] J. Sun, D.D. Klug, R. Martok, J. A. Montoya, Mal-Soon Lee, S. Scandolo, E. Tosatti, PNAS, 106, 6077
(2009).
[18] J. Sun, D.D. Klug, R. Martok, J. Chem. Phys. 130, 194512 (2009); D. Selli, I.A. Baburin, R. Martok,
S. Leoni, Phys. Rev. B 84, 161411 (2011).
[19] T. Ishikawa et al., Phys. Rev. B 77, 020101(R) (2008), Y. Yao, D. Klug, J. Sun, R. Martok, PRL 103,
055503 (2009).
[20] C. Bealing, R. Martok, C. Molteni, J. Chem. Phys. 130, 124712 (2009).
[21] Y. Yao, D. Klug, R. Martok, S. Patchkovskii, Phys. Rev. B 83, 214105 (2011).
[22] L. Hromadov, R. Martok, Phys. Rev. B 84, 224108 (2011).
[23] Y. Yao, D. Klug, Sol. St. Comm. 151, 1873 (2011).
[24] S. Patchkovskii, D. Klug, Y. Yao, Inorg. Chem. 50, 10472 (2011).

[25] Y. Yao, D. Klug, J. Phys. Cond. Mat. 24, 265401 (2012).
[26] Y. Yao, D. Klug, Phys. Rev. B 85, 214122 (2012).
[27] H. Liu, L. Zhu, W. Cui, Y. Ma, J. Chem. Phys. 137, 074501 (2012).
[30] D. Selli, I.A. Baburin, R. Martok, S. Leoni, Sci. Rep. 3, 1466 (2013).
[31] L. Hromadov, R. Martok, E. Tosatti, Phys. Rev. B 87, 144105 (2013).
[32] D. Plaienka, R. Martok, J. Chem. Phys. 142, 094505 (2015).
[33] Tymofiy Lukinov, Anders Rosengren, Roman Martok, Anatoly B. Belonoshko, Computational
Materials Science 107 (2015) 6671.
245
Liquids and glasses at high pressure
and
glassesdeatlahigh
Chrystle Sanloup, Liquids
Institut des
Sciences
Terrepressure
de Paris, Universit Pierre and Marie Curie,
France
Chrystle Sanloup
email: chrystele.sanloup@upmc.fr
Institut des Sciences de la Terre de Paris, Univ. Pierre et Marie Curie, Paris, France
chrystele.sanloup@upmc.fr
Abstract
Liquids and glasses are non-crystalline materials with a preserved short-range order structure.
Structural descriptions at the atomic scale will be given, along with criteria to determine
melting. Measurements of macroscopic properties, such as density, elastic moduli and viscosity
at high pressures will then be described, based on static compression devices (i.e. large volume
presses and diamond-anvil cells). Emphasis will be given on the description of techniques, and
their domain of application. To illustrate the potential of the above-mentioned methods,
research results obtained on the properties of molten silicates, i.e. magmas, over a wide range of
pressures from ambient to the megabar and up to 4000 K, will be presented, and the links
between structure and structure-related macroscopical properties emphasized.
Keywords
Structure, density, viscosity, magmas.

Introduction
Unlike gases and solids, liquids cannot be accurately described, as there is no equivalent to an
ideal crystal lattice or an ideal gas model. Under high pressure (P) conditions, there is no such
thing as a free surface to define the liquid state. Melting can nonetheless be monitored by the
loss of the crystalline long-range order as probed by x-ray or neutron diffraction, and a drop in
viscosity by several orders of magnitude. The former will be evidenced by the concomitant
disappearance of Bragg diffraction peaks and appearance of diffuse scattering (Fig.1).
Figure 1. X-ray diffraction patterns of g-Fe at 2 GPa and 1600 K (black line) and of molten Fe at 2 GPa and 2100 K (grey
line).
246
It is technically challenging to confine a liquid at high pressures as this implies working at high
temperatures (T). Sample surrounding materials must be carefully chosen to minimize chemical
reactions. Larger sample volumes are often necessary compared to their crystalline counterparts in order to have detectable signals. Glasses are melts quenched to room temperature. They
are often studied as a proxy to the liquid state, in which case larger sample volumes are possible
as neither thermal insulation nor heater is required. The same applies to high P amorphous
materials.
This lecture will be organized in two parts. The first part will present the techniques used to
investigate the properties of these non-crystalline materials, along with their domain of
application. These techniques are compatible either with large volume presses (LVP) techniques
and/or diamond-anvil cells (DAC). The second part will be focused on research results obtained
on molten silicates at high pressures, and will illustrate many of the techniques described above.
Physical properties of liquids and glasses: what can be measured and how?
Structural description
Liquids are characterized by a loss of long-range order but they preserve a short-range order (i.e.
first interatomic distances) and a medium-range order (such as polymerization). The shortrange order (a few ) may be probed by scattering techniques, using either neutrons or x-rays.
Non-crystalline materials produce low intensity scattered signals for x-rays/neutron diffraction,
a characteristic that is amplified at high pressures due to the environment surrounding the
sample. The pair distribution function, g(r), that describes the probability to find atoms as a
function of the radial distance, in other words the short-range order, is obtained by Fourier
transforming this scattered signal once normalized into the structure factor, S(q) (Fig. 2, eq.1 and
2).
Figure 2. Sketch of the medium-range order in glasses and melts (A), and short-range order as probed by the radial
distribution fonction g(r) (B).
The equations for S(q) and g(r) are given below for a monoatomic material.
247
S(q) =
g(r) = 1+
where
q=
1
2 2 nr
I(2 )
Af (q) 2
(1)
q(S(q) 1)sin(rq),dq
0
(2)
sin( ) is the scattering vector, l the wavelength, q the Bragg angle, f(q) the
atomic form factor and A a normalization constant such as
limq 0 S(q) = 1.
Under high P conditions, these structural measurements can be done using X-ray diffraction
either in the energy-dispersive mode, as done most often in LVP up to 20 GPa1 or in the angledispersive mode using DAC2. The advantages of EDX are a larger accessible q-range, stronger
beam intensity, and the easier filtering of the background from the high P environment. The
advantages of ADX are a much faster acquisition time, and easier normalization of the structure
factor in monochromatic conditions. Neutron diffraction provides complementary information
to x-ray diffraction, with the possibility to obtain partial distribution functions if using isotopic
substitution3,4.
The medium-range (10-20 ) order is less directly accessible under pressure. The first sharp
diffraction peak (FSDP) that is commonly observed on the structure factor data at low pressures
(below 2 A-1) is an indication of the medium-range order. It can indeed be interpreted as a
pseudo-Bragg peak of quasi-periodic free volumes in glasses and melts5 (Fig. 2A). A notable
effect of pressure is the decrease in intensity of the FSDP, its eventual disappearance, and it shifts
towards higher q-values, i.e. shorter period.
Melting curves
We will focus here on methods that probe melting in volume by opposition to methods that
probe surface properties, such as visual observations of melting (i.e. detection of laser-speckle
pattern for laser-heating DAC experiments or detection of melt textures on the sample surface).
In the case of laser-heated DAC experiments, it should be noted that these bulk methods might
overestimate the melting T, as melting is detected in the bulk but T is measured from surface
emissivity. As mentioned in the introduction, melting can be probed using x-ray diffraction and
is detected by the concomitant disappearance of crystalline Bragg peaks and appearance of a
diffuse scattered signal. This actually described melting of a pure substance. For materials that
melt incongruently, melt and crystals co-exist on the temperature interval between the solidus
and liquidus. In the case of transparent samples, melting may be probed by Raman spectroscopy,
as successfully done on water6 and hydrogen7. Changes in the melting slope are important
indicators of potential structural changes in the liquid phase. Establishing melting curves is also
fundamental in planetary sciences, to constrain internal temperature profiles, and understand
where melts may be present (Fig. 3). Melts are the most efficient carriers of heat and matter
throughout planetary envelopes, they are also the vectors of planetary magnetic fields (i.e. dense
248
liquid hydrogen for Jupiter and Saturn, molten ionic water and ammonia for Uranus/Neptune,
molten iron for the Earth).
Figure 3. Melting curves of H7, H2O6, and silicates8 compared to planetary temperature profiles.
Density measurements
Melting being a first order transition, it is accompanied by a density discontinuity. Glasses and
melts have more compression mechanisms than their crystalline counter parts. Elucidating these
mechanisms first requires accurate density measurements. Pioneer measurements were based
on volumetric methods, either by monitoring the displacement of a piston in a press9 or the
shortening of a reference grid put on the top of a sample in a DAC10. Several methods will be
presented:
- the x-ray absorption method that relies on the Beer-Lambert law:
I
( d )sample ( d )env
=e
I0
where
(3)
I
is the intensity ratio between the upstream and downstream x-ray beam, (r d) is
I0
the density times absorption coefficient times sample thickness product, env stands for the
high P environment. The x-ray absorption method was initially developed to measure the
density of relatively heavy metallic melts such as tellurium11 in LVP, and was successfully
applied later to liquid phosphorous12. The method is DAC compatible13.
- x-ray diffraction method: initially derived for liquid mercury at ambient P14, this method
has been adapted to DAC experiments2. The principle of this method is that the radial
distribution function, F(r), is proportional to the density at distances lower than the first
interatomic distances (equation 4).
249
F(r) = 4 r (g(r) 1) =
q max
q(S(q) 1)sin(qr),dr
0
(4)
the sink-float method consists in inserting a density marker in the sample, and
observing after the experiment on the quenched sample whether the density marker has
floated or sunk in order to bracket the density of the melt15, this method is LVP
compatible.
Compared to crystals, non-crystalline materials have two additional compression mechanisms:
the collapse of the free volume as the latter does not exist in the crystalline forms, and a gradual
increase of coordination numbers versus step increase. When both processes are exhausted,
liquids and crystals tend to have similar compressibilities, i.e. bond compressibility. Structural
changes are not always gradual and first order polyamorphic transitions marked by a density
discontinuity have been reported (e.g. amorphous H2O16, S17, and liquid P12).
Figure 4. Density vs Pressure for amorphous S17 and SiO213 compared to their crystalline counterparts.
Acoustic velocity measurements

Acoustic velocity measurements are a way to get the elastic moduli of materials, i.e. their bulk
and shear moduli, and hence their equation of state (see eq.5 for vp and vs). They are also ideal
measurements in Earth sciences for direct comparison with seismic velocity profiles at depth,
seismic waves being a type of acoustic waves. The major geophysical issues to be solved are the
composition of the lower mantle and the nature of the light elements mixture in the outer core.
vP =
K + 4 /3
and v S =
where K and m are respectively the bulk and shear moduli, and r the density. Three techniques
will be presented:
250
(5)
acoustic velocities can be directly measured on compressed non-crystalline materials by

recording propagation time of ultrasonic waves through millimetric samples in LVP up
to 25 GPa18.
Brillouin spectroscopy consists in the inelastic scattering of a laser light, and the
acoustic velocity is then proportional to the energy variation (eq.6); it can only be used
for transparent samples in DAC; record measurements have been obtained on liquids
for water up to 200C and 4 Gpa19 and on glasses at room T to almost 200 Gpa20.
v=
-
dE
with E the energy and q the momentum transfer
dq
(6)
inelastic X-ray scattering works in a similar way to Brillouin spectroscopy but using xrays instead of visible light, therefore at much higher energies, the advantage being that
IXS is not restricted to transparent samples; record measurements have recently been
done on molten Fe-alloys up to 70 GPa and 3000 K using laser heated DAC21.
Viscosity measurements
Viscosity measurements under pressure are a way to understand how particle or molecular
interactions evolve as a function of density. They are also important for lubrication applications,
and for dynamical models where pressure is involved. Pioneered by P. Bridgman22, viscosity
measurements are now routinely carried out on liquids up to 10-15 GPa using large volume
presses. As in Bridgman set-up, the method still consists in measuring the speed of a free falling
sphere in the liquid that obeys the Stokes law. Imaging of the free falling sphere is done by
recording x-ray radiographic images through the cell-assembly, ideally using a white x-ray beam
to enhance beam intensity and consequent imaging contrasts. High speed cameras now allow
the study of extremely low viscosity melts (i.e. water, carbonate melts with viscosity of only a few
mPa.s23).
2gr 2 (sphere fluid )W

9vE
(7)
where is the viscosity, r the radius of the falling sphere and v its speed, W and E are correction
factors that account for the wall and end-effects of a finite cylindrical container. This method is
also compatible with diamond-anvil cells24 in a similar P range, the limitation coming from the
narrow space available between the anvils. Due to important wall effects, the rolling ball
technique is preferred to the falling sphere, with as a draw-back that viscosity can only be
measured relative to its ambient P value.
The expected behavior under increased P is an increase of viscosity following the reduction in
free volume. However several materials including water22 display otherwise. This is due to
changes in particle interaction in relation with important structural changes that affect their
viscosity. Measuring viscosity at P exceeding 15 GPa is one of the current technical challenges in
the high pressure field. Optical tweezers, whereby a laser beam manipulates a solid bead and
following its motion, have been used in conjunction with DACs to measure the viscosity of water
251
up to 1.3 GPa25. This DAC-compatible method opens up perspective to investigate much higher
P.
Insights into the properties of magmas at depth
This research part will present results obtained on magmas, i.e. molten silicates, at the
conditions of their formation, ascent and eventual segregation at depth. Magmas are essentially
high-pressure objects, being formed at depth. In the present-day Earth, magmas that erupt at the
surface were formed at depth ranging from 10 to 50 km below mid-oceanic ridges, down to 150
km below subduction-related volcanism. Seismological observations also reveal locally the
presence of magmas at discrete depths such as below the lithospheric plates, atop the main
mineralogical transition zones, and at the bottom of the mantle. Magmas are ubiquitous objects
in the solar system, both currently on the surface of terrestrial planets and some satellites (e.g. Io,
the Moon), and in the past as planets were born molten. The structure of planets as we know
them now has thus been inherited from this molten era, the magma ocean stage. Matter and heat
were transferred through the magma ocean either to the surface or to the core of planets, density
exerting a first order control on these differentiation processes.
Density measurements
The compressibility of magmas has been measured extensively at ambient P using ultrasonic
techniques26, resulting in a comprehensive data-set. First high P density measurements on
magmas were obtained with shock-wave techniques up to 23 GPa27, verifying the prediction of a
density cross-over between melts and co-existing crystals28. The existence of melts/crystals
cross-over(s) imply that magmas may be trapped at depth. This major result has been confirmed
by static high P-T sink-float measurements29. Basalts are the most common magmas produced
on Earth (>95%). Their density and structure have been measured down to lower mantle
pressures30 using the x-ray diffraction method (fig. 5). It is thus possible to draw some
conclusions on their compression mechanisms.
Figure 5. Density of molten basalt30 as a function of pressure, compared to the PREM seismological profile (green
curve), to theoretical calculations (grey curves) and to shock-wave data (dashed grey curve).
252
Densification mechanisms
At ambient P, the basic unit of silicate melts, i.e. the [SiO4]4- tetrahedron, persists in the molten
state as the basic structural unit. It polymerizes as rings, unless the SiO2 content of the melt is
too small (33 at %). The rings statistics, i.e. percentage of rings of a given size, are now well
defined on glasses at ambient P using SEM imaging techniques. Under high pressures, indirect
methods are Raman spectroscopy and the first sharp diffraction peak observed on scattered
intensity data (either neutrons or X-rays). The three following mechanisms will be illustrated:
- collapse of the ring structure below 5 GPa, a thermally-induced mechanism therefore occuring
at lower P in melts than in glasses.
- increase of coordination number for the main cations (Si, Al, Mg, Ca, Fe), a mechanism
affecting melts and glasses similarly (Fig.6).
- bond compression, similar to glasses, melts, and crystalline phases.
Figure 6. Silicon coordination change in melts and glasses (right) and in crystalline Mg2SiO4 (right).
The planetary implications are two-fold. First, magmas can be trapped at the bottom of the
upper and lower mantles, providing they can be produced. Second, the magma ocean could have
consisted of two molten layers separated by a crystalline layer based on gravitational arguments.
Such a configuration had been proposed based on thermal arguments, as a single magma ocean
should have cooled down within 1 Myr, a timescale 2 orders of magnitude shorter than the
formation of the core (circa 50-100 Myrs) taken as a proxy of the magma ocean lifetime.
Viscosity of molten silicates
At low P, the viscosity of silicate melts is strongly controlled by their degree of polymerization,
itself a function of the SiO2 content. Under increasing P, the viscosity drops, an effect clearly
demonstrated for SiO2-rich compositions that are the most affected (see ref32 for a review), but
the viscosity drop also affects the most depolymerized compositions33. This decrease in viscosity
is likely related to the decrease in voids volume and their eventual collapse. However, viscosity is
expected to raise above 10 GPa, an effect that remains to be measured.
253
Conclusions
Tremendous progresses have been done in the field of high P studies of liquids and glasses over
the last decade, in relation with technological developments at x-ray synchrotron facilities and
neutron sources. If measuring their viscosity, the physical parameter that essentially
distinguishes a liquid from a solid, is still a challenge above moderate pressures, measuring their
structure, density and elastic properites is now possible up the megabar scale.
Acknowledgments
The author acknowledges synchrotron facilities for provision of beamtime (PetraIII, APS,
Diamond, ESRF) and beamline scientists for their precious help (Z. Konopkova, Y. Kono).
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255
Techniques for materials discovery and optimized HP synthesis
Techniques
for materials
discoveryDepartment,
and optimized
synthesis
John B. Parise, Department
of Geosciences
and Chemistry
StonyHP
Brook
University,
Stony Brook, NY 11794-2100, USA; Photon Sciences, Brookhaven National Laboratory, Upton
John B. Parise
NY 11973, USA
Dept of Geosciences and Chemistry, Stony Brook Univ., Stony Brook, NY, USA; Photon
email: john.parise@stonybrook.edu
Sciences, Brookhaven National Laboratory, Upton,NY, USA
john.parise@stonybrook.edu
http://www.stonybrook.edu/commcms/geosciences/people/faculty/parise/index.html
www.stonybrook.edu/commcms/geosciences/people/faculty/parise/index.html
Abstract
The application of pressure in solid-state synthesis provides a route for the creation of new and
exciting materials. However, the onerous nature of exploratory solid-state synthesis using large
volume high-pressure techniques limits their utility in materials discovery. The systematic
search for novel semiconductors for photocatalytic overall water splitting is a representative case
where quench high-pressure synthesis informed by theoretical calculations is useful, and
sometimes necessary, in order to efficiently identify and synthesize target compounds. The
increasing availability of community-based databases and ab initio theory provides new
opportunities for structure search based on desired properties, such as band gap and band edge
position. By employing in situ synchrotron techniques, synthesis target lists can be rapidly
surveyed to speed up the discovery and optimization of novel compounds. In a case studies, the
prediction, synthesis and characterization of novel phases in the Nb2O5-GaN, are presented.
Keywords
High-pressure synthesis, structure prediction, crystal structure, property prediction

Introduction
High pressure (HP) can be a key variable1 for materials discovery and is underutilized relative to
exploratory solid-state chemical synthesis at ambient pressure2,3 . Despite its perceiveed
specialist nature, pressure tuning along with serendipitous and theory-guided strategies, provide
exciting avenues for the discovery of novel solid-state materials at HP. Given the installed
industrial infrastructure for the production of diamond, useful materials produced in the
"industrial zone", say P < 7GPa, would be particularly appealing. The specialized infrastructure
that is required for large volume HP exploratory synthesis limits its utility in the laboratory
setting. Further, the slow throughput implied by the need to perform individual quench
experiments to cover high-pressure and high-temperature (HP-HT) phase space, conspire to
limit the use of HP exploratory synthesis3. Exhaustive coverage requires months of work using
cook-and-look quench recovery experiments. On the other hand, recent successes in
producing novel materials inspired by theory4-13 suggest collaborations employing crystal
structure prediction to identify P-T conditions under which a target phases is stable, when
combined with in situ observation of reactions at synchrotron and neutron sources14-17, will
facilitate and expedite HP materials discovery in the future.
256
Historically computational methods have been ineffective in predicting reaction conditions and
the structure of inorganic solids, and commentary on this problem has ranged from labeling it a
"scandal,18 to the somewhat more helpful suggestion that, although we cannot not as yet
proceed ab initio from desired property to functional material, we can proceed incrementally
toward this goal.19 In the three decades since such commentaries, there has been sustained and
fruitful progress in computational materials discovery, which include fully non-empirical global
optimization searches, such as employed by the USPEX method,20,21 and data mining
techniques.22-25 These approaches are complementary.
Overall approach
A rational approach to materials design involves 1) Defining a desirable property, 2)

determining26 compositions, and structure-types likely to give rise to those properties, 3)
quantifying the desirable properties and HP stability ranges to rank order the synthesizability, 4)
synthesizing the predicted compositions and verifying their structures in-situ in order to provide
feedback to theory and 4) producing materials in, either from HP quench experiments or soft
chemistry at ambient pressure27, for testing. The first three of these steps are common to all
materials discovery. In the case of a phase being stable at close to ambient pressure, a low hit-tomiss ratio can be compensated for using combinatorial synthesis techniques28 and the structure
and properties of many compositions are simultaneously investigated. A low hit-to-miss ratio is
very problematic if one can only explore say two p-T points per day, as is the case in most HP
quench-recovery experiments. To realize the full potential of the HP variable to produce
transformative materials requires an approach that combines: (1) Prediction, using all tools and
approaches including database search22 that emphasizes deriving properties as well as predicted
structures, and ab Initio techniques to determine pressure stability ranges for target
compositions; both approaches are clearly complementary and serve to narrow the
compositional search range, to derive trial structures, properties and stability ranges. (2)
Discovery of new materials is optimized by using HP apparatus coupled to synchrotron x-ray
and neutron sources; after confirming the predicted phases are indeed not stable at ambient
pressure, rapid survey of p-T space by looking inside pressure vessels accelerates materials
discovery and provides an immediate test of theoretical predictions. (3) Characterization of the
properties and feedback to theory. While solid-state chemical principles, intuition and
serendipity will continue to produce novel materials, more systematic approaches incorporating
learning, data mining and ab Initio theory will provide a framework for discovery of novel
materials that will be applicable to the HP synthetesis in general. By making HP a component of
a wider enterprise - such as the Materials Project (MP) Platform29,30 - the results of these
approaches can be widely shared.
Photocatalysts: Anticipated Advantages of High-Pressure Synthesis
Photocatalysis, and overall water splitting by oxides and oxynitrides provide an opportunity to
demonstrate the overall strategy for HP materials discovery and synthesis because of: 1) their
257
relative water stability compared to chalcogenides, for example, 2) evidence that nitride
substitution leads to narrowed band gaps31 that can be tuned for optimal performance , 3) both
groups, especially oxynitrides, are relatively under explored at HP31 and their theory-directed
synthesis provides materials rich in new phenomena31, 4) HP stabilizes reactants which tend to
decompose at ambient p and high T32 and pushes equilibria toward the solid rather than gaseous
(N2, O2) alternative products and 5) compared to ammonolysis or variable oxygen-pressure
routes, using closed systems at HP offers a facile route to dial in stoichiometry, and perhaps
O/N order/disorder in solid solutions.
Introduction to semiconductor driven solar water splitting
Figure 1. Basic principle of overall water splitting on a heterogeneous photocatalyst33.
The shift toward a renewable energy economy will require breakthrough technologies to
efficiently and economically collect and store solar energy. Semiconductor driven solar water
splitting by inorganic materials can potentially meet these goals via the conversion of solar
energy to chemical energy (H2 fuel). Under irradiation at an energy equivalent to or greater than
the band gap of the semiconductor photocatalyst33 (Fig. 1) electrons are excited into the
conduction band, leaving holes in the valence band that, if not recombined, are available for
reduction (e-) and oxidation (h+). To achieve overall water splitting, the absolute value of the
band gap, and positions of the band edges must be appropriate. Specifically, the gap must be
sufficiently small to absorb a large portion of the illuminating light, the conduction band edge
absolute energy must be high enough for electrons to reduce H+ to H2 and the valence band
edge absolute energy must be low enough for holes to oxidize the oxygen in H2O. While
empirical screening work34-36 has had its successes, combinations of property-driven database
search25,26, and metadynamics17 to identify target compounds and the energy landscape they
inhabit, will ultimately prove more successful.
258
The growth of reliable DFT calculations and the coupling of these to experimental approaches
seems particularly advantageous in the case of band gap engineering for energy conversion and
storage22-24,26,33,37-39. Oxides and oxynitrides are of current interest because of their potential to
complement31 and in some cases surpass33 properties of existing oxide photocatalysts. Because
oxygen and nitrogen have similar polarizabilities, electronegativity, and ionic size, there are
several crystal classes that share the same structure type31, and this can be used in database
search approaches26. We propose a comprehensive effort to discover, understand and improve
new and existing oxide and oxynitride semiconductors for solar water splitting, based on indepth characterization of their bulk properties using the theoretical and in-situ and ex situ
experimental expertise of our team. The influence of band edge absolute energies on the
performance of these compounds will also be specifically investigated, using chemical tuning, via
the formation of solid solutions.
The theory-in-situ-diffraction-feedback and improved theory strategy is in its infancy, and
several chemical features, such as surface reconstruction 40, solid solution 41, and disorder are
already recognized as complicating factors. However ultimately, closing the loop by feeding back
experimental results will improve prediction.
Structure, band gap, band edge prediction
The methodology for the prediction of compositions and structures suitable for overall
photocatalytic water splitting is explained in reference26. In a limited investigation, candidates
for screening are generated from oxynitrides of d10 and d0 cations33,42 from databases of structures
such as the Inorganic Crystal Structure Database (ICSD). This approach uses information about
the substitution probability of ions obtained by data-mining all experimentally known
crystalline compounds to provide structure suggestions for the design of novel compounds.
Using the set of all known binary ionic compounds as a starting point, new quaternary
compounds (M1M2ON with M1 or M2 being a d0 or d10 cation for example33,42), known
ternary oxide photocatalysts can be used as the structural framework on which to perform the
substitutions. For instance, SrTiO3 could lead to a new candidate from substituting Sr2+ by La3+,
Ti4+ by Ta5+, and O2- by a mixture of N3- and O2- according to a probabilistic model. The amount
of O and N to be substituted in each compound was determined by balancing the charge of the
cations. There is however still a remaining degree of freedom in the exact ordering of O2- and N3on the anion sites. These orderings can be enumerated and selected according to which ones
lead to the smaller cells and the larger number of NN bonds, as the ordering of oxynitride
anions has been recently shown to be driven by this factor43,44. For each candidate compound,
DFT calculations were carried out for all selected orderings and only the one with lowest energy
was considered.
Evolutionary Algorithm approach.
Evolutionary algorithms45,46 mimic Darwinian evolution genetic crossover, mutation, and
natural selection of the fittest. Such algorithms are known to be very efficient in finding global
259
minima of multidimensional functions and are used in many areas of science and technology45,46.
Within this general scheme, a great multitude of very different algorithms can be devised, and
USPEX20,21 was a significant step forward, providing a practical recipe for affordable firstprinciples prediction of complex structures. The accuracy of predictions depends critically on
the accuracy of the underlying energy calculations and structure relaxation. Calculations are
done in the framework of DFT, by interfacing USPEX external codes. USPEX is interfaced with a
number of well-known simulation codes, including VASP47, SIESTA48, GULP49, CP2k, and
Quantum Espresso50. These codes are used for structure relaxations and energy calculations.
GULP enables cheap calculations based on a variety of parameterized interatomic potentials,
while VASP, SIESTA, CP2k and Quantum Espresso employ state-of-the-art density-functional
techniques and give accurate results for many classes of compounds at a higher, but still
affordable, computational cost. With the caveats noted below, DFT calculations provide good
accuracy of structural and thermodynamic properties. While straightforward extension allows
the prediction of solid solutions, as often exist in oxides and oxynitrides21,51, the inclusion of
disorder in multicomponent systems such as the oxynitrides is computationally expensive and a
key area for future improvement.
Synthesis and characterization using ex situ and in-situ X-ray scattering
In-situ x-ray enhances our ability to efficiently search for new predicted materials and to confirm
their predicted HPT stability fields, and structures. Several International facilities now host large
volume HP devices interfaced to x-ray synchrotron sources.
Case study: structure prediction and synthesis in the (GaN)x (Nb2O5)y system
Using the evolutionary algorithm as implemented in USPEX52-54 a variable-composition search

was performed to generate a range of compounds with initial chemical compositions chosen at
random from a mixing of GaN and Nb2O5 endmembers. This population of structures, and their
compositions, then evolved with the help of variation operators (among which, transmutation
and heredity are composition-changing, and lattice mutation and soft-mode mutation are
composition-conservative).
Figure 2. Predicted enthalpies of formation for GaN Nb2O5 compounds at ambient pressure (left) and 20 GPa (right).
The circles represent individual structures and are plotted as compositions versus enthalpies of formation.
260
Figure 3. Lowest energy GaNb2O5N structure predicted to be stable at 20 GPa. Gallium (orange) is coordinated by 6
oxygen atoms in a distorted octahedra while niobium (green) is coordinated by 7 oxygen atoms and 2 nitrogen atoms in a
tricapped trigonal prism geometry. Unit cell is outlined with dashed blue line.
All the generated structures were relaxed and then ranked according to their fitness, with only
the fittest 60% of each generation allowed to produce the next generation of structures. The
underlying ab initio structure relaxation and electronic structure calculations were carried out
using the all electron projected augmented wave (PAW) method55 as implemented in the Vienna
ab-initio simulation package (VASP).47 The Perdew-Burke-Ernzerhof (PBE) functional was used
to treat the exchange-correlation energy.56 A plane-wave kinetic cutoff energy of 600 eV was
used in addition to reciprocal space sampling with dense Monkhorst-Pack k-point meshes57 at a
resolution of 2 x 0.05 -1 in order to provide sufficient accuracy during enthalpy calculations.
Variable-composition structure prediction calculations in the (GaN)x (Nb2O5)y system were
performed at 0 and 20 GPa to evaluate the stability of oxynitride compounds encountered. While
the commercial zone of high-pressure is most desirable (<6 GPa) for potential in scale-up
production, the calculations need to be conducted at a significant overpressure to compensate
for the 0K temperature of the calculations. At 0 GPa, the calculations indicate all of the predicted
compounds are unstable and decomposition into the endmembers wurtzite GaN and R-Nb2O5 is
energetically favored (Fig. 2 - left). However, calculations at 20 GPa indicate a stable oxynitride
with a composition of GaNb2O5N as the enthalpy of formation is lower than that of the end
members wurtzite GaN and Z-Nb2O5 (Fig. 2 - right). The structure of the predicted ordered
GaNb2O5N phase is shown in Fig. 3. The 20 GPa calculations indicate a high probability of a
reaction occurring at HP, although the predicted structure did not match that of either of the
oxynitride phases found in the HPHT experiments.
In-situ HPHT XRD Investigation of (GaN)(Nb2O5)
The HPHT reaction between GaN Nb2O5 was studied in situ at pressures and temperatures up
to 3.8 GPa and 1200C using energy dispersive XRD (EDXRD) at the X17B2 beamline at the
National Synchrotron Light Source (NSLS). A 1:1 mix of GaN and Nb2O5 (99.99%, SigmaAldrich) was mechanically ground in an agate mortar and pestle for 45 minutes and loaded into a
BN sleeve. The mix was stacked on top of an MgO internal pressure standard and physically
separated with a layer of BN powder. The sleeve was inserted into a boron epoxy cubic DIA cell
261
with a resistive heating graphite furnace and a W-3%Re/W-28%Re thermocouple (Fig. 4). The
cell was compressed using a 1000 ton multi-anvil press (BAM11) and the EDXRD patterns were
collected using a white beam (14-120 keV X-rays) incident on tungsten slits to produce a 100 m
x 100 m beam. The cell was first compressed to a press loading of 15 tons (~1 GPa) and the
temperature was raised to 1000C with EDXRD patterns collected every 100C with 300 s
exposure after a 1000 s reaction time.
Figure 4. Cross section of the cubic cell assembly (left) used at the X17B2 beamline at NSLS and the 19 mm diameter
piston cylinder cell assembly (right). The cubic assembly measures 6.35 mm on each side and the overall length of the
piston cylinder assembly is 4.45 cm.
Figure 5. In situ EDXRD patterns of a 1:1 mixture of GaN and Nb2O5 at a constant press loading of 15 tons. The EDXRD
pattern of the initial GaN:Nb2O5 mixture at ambient pressure and temperature is at the bottom of the figure in black and
contains peaks attributed to only wurtzite-type GaN and monoclinic Nb2O5. Upon pressing the sample to 1.2 GPa and
heating to 600C and 700C, the Nb2O5 underwent a phase transformation to the orthorhombic phase but did not react.
At ~800C however, the XRD pattern undergoes a drastic change indicative of a reaction, highlighted by the decrease in
intensity for the major GaN (101) refection as the rutile structured oxynitride phase forms. The reaction is essentially
complete by 1000C, with only minor GaN left unreacted.
The cell was then cooled to room temperature, followed by an increase in pressure to 25 tons.
The temperature was then raised in 100C increments to 1200C with the same EDXRD data
262
collection strategy described above employed at the end of each increment with the process
again repeated at 35 tons.
Figure 6. In situ EDXRD patterns of GaN Nb2O5 reaction at a constant press loading of 25 tons. The rutile oxynitride
phase remains the only Ga-Nb oxynitride phase in the pattern as the sample is heated to 800C. At 900C, the intensity of
the rutile type (211) and (220) reflections begin decreasing and new peaks in the pattern are apparent by 1200C,
belonging to the new -PbO2 type oxynitride phase.
The EDXRD results of the in situ HPHT reaction study are summarized in Figs. 5, 6 and 7. At
approximately 1 GPa, we observe the onset of a reaction between GaN and Nb2O5 at 800C as
noted by a complete restructuring of the XRD pattern and a diminishment of the (101) GaN
reflection (Fig. 5); the reaction is complete by 1000C. The new Ga Nb oxynitride observed at ~
1GPa has major reflections in the EDXRD patterns at approximately 1.74 (211) and 1.64 (220),
consistent with a rutile type (TiO2) structure (described below). At ~ 2.8 GPa and 900C, the
intensity of peaks attributed to the rutile type phase begin to diminish as new reflections
belonging to a -PbO2 type structure appear, indicative of a phase transition (Fig. 6). Moreover,
as the sample temperature is increased past 800C at 3 4 GPa, the phase transition continues
with an increasing intensity of the -PbO2 reflections but without the complete disappearance of
reflections attributable to the rutile type phase (Fig. 7).
The EDXRD patterns of the in situ HPHT investigation revealed two novel oxynitride phases
existing in the GaN Nb2O5 system below 3.8 GPa and 1200C. The EDXRD patterns indicate
the optimal conditions for the quench synthesis of the rutile and -PbO2 type phases are 1 GPa
and 1000C, and 3.8 GPa and 1200C, respectively. As the piston-cylinder apparatus is limited to
P 3 GPa, the quench experiment targeting the -PbO2 phase was conducted at 3 GPa and
1200C in order to maximize the amount of this phase in the sample.
The in situ studies of the GaN Nb2O5 reaction mapped phase stability in P-T space and
provided the optimal reaction temperatures for synthesis, thereby limiting the number of
263
quench experiments required to recover the high-pressure phases to two. This represents a
considerably higher success rate than could be realized from the use of single P-T quench
exploratory synthesis. Multi-anvil press assemblies at user facilities offer fast and extensive
evaluation of reactions at industrially viable pressures and temperatures. Cell assemblies can also
be made to house two different reactions with a pressure calibrant to speed up P-T exploration
even further. With this experimental setup, two chemical systems can be evaluated up to modest
pressures and temperatures (~5 GPa and 1500C) in a period of 24 hours. The alternative
process of conducting several quench-recovery experiments followed by the characterization of
recovered phases to map P-T space could require weeks or months of work.
Figure 7. In situ EDXRD patterns of GaN Nb2O5 reaction at a constant press loading of 35 tons. Following the trend at
25 tons, as the temperature is increased, we see a decrease in the intensity of the rutile type phase (211) and (220)
reflection and the new peaks belonging to the -PbO2 type phase increase in intensity through 1200C.
Structural characterization
The product of the 1 GPa - 1000C quench experiment from a piston cylinder using a modifies
cell assembly (Fig. 4) was evaluated with both high-resolution XRD and TOF powder neutron
diffraction. After known phases were identified, the new oxynitride phase in the XRD pattern
was indexed, its crystal structure solved, and a Rietveld refinement conducted with the program
TOPAS (v4.1, Bruker AXS). Because of the large X-ray scattering contrast between Nb5+ and
Ga3+, the occupancies of Nb5+and Ga3+ on the single metal site were refined, with the constraint
that the total occupancy of the site is 1.0.
The X-ray scattering contrast between O2- and N3- on the other hand is small, and so neutron
diffraction data were collected on the same sample as the neutron scattering contrast is high (bO
= 5.803 fm; bN = 9.36 fm) and can resolve the O/N occupancy and any possible ordering on the
anion site. A structure model was refined using two TOF frames and the GSAS/EXPGUI
Rietveld software package.58,59 As Nb5+ and Ga3+ have nearly identical neutron scattering lengths
264
(bNb = 7.054 fm; bGa = 7.288 fm), the rutile type metal site was fixed to the ratio determined from
the XRD refinement. The occupancy of O2-and N3- on the anion site was allowed to freely refine
(constrained to add to 1). Using the refined occupancies on both the cation and anion sites, the
chemical formula for the rutile related phase is Nb1.41Ga0.58O3.41N0.59. To satisfy charge balance,
this formula implies some reduction of Nb5+ or the existence of vacancies in the site occupied by
Nb/Ga, or both. In the case of Nb5+ reduction, the composition may then nominally be
represented as (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82. No additional, superstructure peaks could be
detected in either data sets indicating that both the anion and cation sites were indeed
disordered. The refinement details and crystallographic data for the rutile relate phase is
available in the literature. 16 The synthesis at 3 GPa - 1200C yielded approximately 50 mg of
sample used to collect a high-resolution powder XRD data (Fig. 8). A Rietveld refinement using
TOPAS revealed three phases - major rutile type, and minor -PbO2 type in addition to GaN
(Fig. 8). The oxide phases of GaNbO4 and Nb2O5 that were present in the lower pressure (1 GPa)
sample are notably absent and have participated in the reaction at 3 GPa.
Fig. 8. XRD Rietveld refinement result of a sample synthesized at 3 GPa - 1200C and containing contributions to the
diffraction pattern from rutile type phase, -PbO2 type phase and unreacted GaN. The collected pattern is shown in
blue, the calculated pattern in red, and the difference in black. The vertical tick marks below the difference pattern show
the positions of reflections of the respective phases; starting from the top, red markers represent positions for reflections
from rutile type phase, green for -PbO2 type phase and blue for GaN.. The inset compares the largest reflection of the
rutile type (110) with that of the -PbO2 type (111). For the (110) reflection there are eleven tickmarks belonging to
distribution of phases used to model variable composition of the rutile-type phase.
The rutile type phase in the sample has a large asymmetric peak shape likely due to chemical
inhomogeneity during the slow phase transition to -PbO2 type phase, which was modeled as
eleven rutile phases, with a constrained distribution of tetragonal lattice parameters (Fig. 8
inset). Due to reflection overlap, the the actual occupancy of Ga and Nb in these phases cannot
be accurately determined. However, trial refinements hinted at a difference between the rutiletype phases recovered in the 1 GPa and 3 GPa samples. For example, while the 1 GPa sample
contains a single rutile-related phase with Nb-occupancy of ~0.7 (Table 1), the fits of the
distribution of rutiles in the 3 GPa sample indicated the same Nb occupancy of ~0.55 across the
whole distribution. This suggests that the inhomogeneity is predominantly in the O/N site and
265
that this is changing as the lower pressure rutile phase gradually transforms to the HP phase.
The refinement and crystallographic details of the rutile and -PbO2 type phases are show in
Table 1.
Table 1. Summary of the results of Rietveld refinements for 1- and 3-GPa phases.
Rutile-Type (Neutron)*; sample quench recovered from 1 GPa, 1000C (Fig. 8)

Atom
Uiso X 102 (2)
0.0
0.0
0.0
1.22(4)
0.2950(2)
0.2950(2)
0.0
1.19(3)
-PbO2-Type (X-ray)**; sample quench recovered from 3 GPa, 1200C (Fig. 9)

M
0.0
0.1749(2)
0.25
1.0(2)
0.2694(9)
0.3864(7)
0.4201(9)
0.4(1)
*Space group P42/mnm, a = 4.7294(1), c = () 4.7294(1), V = 67.573(1) 3, wRp = 0.119, 2 = 1.63; M occupancy Nb =
0.71(1)
Ga = 0.29(1) determined from refinement using the x-ray data. ** Space Group Pbcn, a = 4.6363(1) , b =
5.5947(1) , c = 4.9780(1) , V = 129.122(1) , wRp = 0.138, 2 = 1.51; A occupancy O = 0.856(3)

determined from refinement using the neutron data (see text).
N = 0.144(3)
Optical Properties of Rutile Type Oxynitride

The optical properties of the rutile-structured oxynitride were evaluated using UV-VIS-NIR
diffuse reflectance to determine whether the band gap was suitable for water splitting
photocatalysis. Relative absorbance (KM) was generated using a Kubelka-Munk transform and
was fit using the same band gap functional fitting methods used to study the optical properties of
(GaN)1-x(ZnO)x nanorods and nanocrystalline gallium oxynitride spinel.27,60 The optical fitting
revealed a contribution from a direct band gap of 0.84 eV as well as an indirect band gap of 0.51
eV.
The optical data and band gaps are consistent with the black color of the powder as it absorbs
through the visible range. The short band gap is unexpected as the respective oxide, GaNbO4, is
a wide band-gap semiconductor.61,62 However, a HPHT reaction of Ga2O3 and Nb2O5 at identical
synthesis conditions (1 GPa, 1000C) produced a black powder of wolframite type GaNbO4.The
color in both the HPHT oxide and oxynitride is likely due to partial reduction of Nb5+ to Nb4+,
and the chemical formula derived from neutron refinement is consistent with this conclusion.
Acknowledgments
Theoretical calculations, synthesis, and analysis were supported by NSF-DMR-1231586. X17B2

at NSLS was supported by DOE DE-AC02-98CH10886 and COMPRES (NSF-EAR 10-43050).
The high-resolution XRD was supported by the DOE Contract No. DE-AC02-06CH11357 to
266
APS. The neutron scattering measurements at POWGEN at SNS were supported by the DOE
contract DE-AC05-00OR22725.
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and chalcogenides. Acta Crystallogr., Sect. A: Found. Crystallogr. 32, 751-767 (1976).
269
High pressure crystallography of metal-organic frameworks (MOFs)
High
pressure
of Photon
metal-organic
frameworks
(MOFs)
Karena W. Chapman,
X-ray
Sciencecrystallography
Division, Advanced
Source, Argonne
National
Laboratory, Lemont, Illinois, 60439, USA
Karena W. Chapman
email: chapmank@aps.anl.gov
X-ray Science Division, Advanced Photon Source, Argonne National Laboratory,
homepage: http://www.aps.anl.gov/About/People/Detail/?name=Karena__Chapman
Lemont, IL, USA
chapmank@aps.anl.gov
www.aps.anl.gov/About/People/Detail/?name=Karena__Chapman
Abstract
In the last 25 years, metal-organic frameworks (MOFs) have become an important class of
crystalline materials, with widely varied structures, functionalities and potential applications.
While the high pressure behavior of these materials has only recently been explored, this handful
of studies have demonstrated a rich variety of pressure-induced phenomena in these flexible
frameworks. These phenomena occur at much lower pressures than are typical for solid-state
materials, including at pressures that can be readily achieved on a bulk scale. The often porous
nature of these framework materials adds richness to their high pressure behavior, with the
potential for molecules to move between the pores and the surrounding fluid. The low pressure
ranges at which transitions can be induced and their coupling to porosity opens exciting new
possibilities to manipulate the structure and properties of these emerging materials systems.
Keywords
Porosity, Phase transitions, Amorphization, Negative Compressibility, Host-guest phenomena

Introduction
Metal-organic frameworks are an important and growing class of crystalline solid materials with
diverse structures, chemistry and functional properties. Their framework architectures are
formed from metal ion or cluster nodes that are bridged by organic struts to form an extended
periodic lattice. The framework itself, with directional bonding-interactions between extended
building blocks, does not fill space efficiently and, as such, often defines a network of welldefined pores which can contain guest molecules. This nanoscale porosity, and the associated
high internal surface area, is the basis for the many potential applications being explored for
MOFs, including for molecular/gas storage and separations, catalysis, guest-dependent
functional behaviors.
Due to their porosity and low density, the structure of MOFs can be particularly sensitive to
pressure. With even small changes in MOF structure able to produce disproportionally large
changes in functional behavior, pressure can substantially modify MOF functionalities.
Consequently, the exploration of MOFs at pressure is not only of fundamental interest but is
relevant to the realization of MOF-based technologies. Interesting high pressure behaviors
documented to date in MOFs span high compressibility, anisotropic compressibility, negative
linear compressibility, crystalline phase transitions, amorphization transitions, reconstructive
270
transitions, volume expansion transitions, guest uptake/exchange, and electronic state switching
of the metal center.
MOF structure and synthesis
Metal-organic frameworks consist of metal ions (or clusters) and molecular ligands connected in
an infinite periodic array via coordination bonding. The individual components self-assemble
from solution, with the resulting architecture dictated by straightforward geometric
considerations related to the directional bonding and intermolecular interactions.
The choice of metal nodes and organic linkers dictate the structure and properties of the MOF.
Nodes can be individual metal ions or metal-complex clusters. Struts or linkers include di-, triand tetra-pyridyl and carboxylates organic ligands. Often, these organic molecules are highlyconjugated aromatics, which imparts rigidity to the ligand.
Not only does the modular nature of MOFs allow for a large variety of complex structures to be
generated from a small library of relatively simple components, but it allows for the MOF
structures (and functionality) to be rationally tailored towards specific applications by
systematically modifying individual components. For example, the well-recognized series of
isoreticular MOFs based on the MOF-5, all feature an (OZn4)O12 cluster connected via linearly
bridging di-carboxylates ligands to form a cubic network. In the archetypal MOF-5 system, these
Zn-cluster nodes are bridged by 1,4-benzendicarboxylate ligands. By changing this ligand, for
example, by using functionalized 1,4-benzendicarboxylates or longer aromatic dicarboxylates, a
broad series of MOFs with the same topology but different surface functionality or pore size can
be generated (see Figure 1)
Figure 1. The modular construction of MOFs allows for a diverse range of structures and topologies to be accessed from
a small library of components. The IRMOF series, based on the architypal MOF-5, is formed by Zn-oxide based clusters
bridged by dicarboxylateb-based ligands. A consequence of the extended nature of the framework components is that the
framework itself fills space inefficiently and often defines voids, indicated by spheres, within the crystal volume.
Many individual MOFs are named for that institution where there were first synthesized.
Examples include HKUST-1 from the Hong Kong University of Science and Technology, the
UiO series from University of Oslo, and the MIL series-Materials of the Institute Lavoisier. The
class of MOF and MOF-like materials are alternatively known as coordination framework
271
materials, molecular framework materials, coordination polymers, and organic-inorganic hybrid

materials, with the term "metal-organic framework" now being most widely recognized. While
each term may define subtly different, overlapping sub-sets of framework materials, the points of
distinctions are not particularly relevant to their high pressure behavior.
Compared to traditional solid-state materials, based on corner-, edge-, and face-sharing
polyhedra, MOFs have greater structural and chemical versatility, with more open structures,
and more structural degrees of freedom. With expanded structural building components
molecular ligands in place of single atom (e.g., -O-, -F-, -S-) bridgesand highly directional
bonding interactions, the MOF framework itself often fills space inefficiently with low
framework density. This framework defies voids in the crystal volume, a pore network, in which
non-coordinated "guest" molecules can reside or independent, non-coordinated frameworks
interpenetrate.
A further consequence of MOFs' expanded network structure is that they can tolerate a wide
variety of different structural distortions and displacive transitions without disruption of the
overall framework connectivity and topology (Figure 2). Evidence of the wide range of
geometries that can be tolerated by the MOF structures can be seen in many of the
dicarboxylate-based "MIL"-systems, where variations in the angle subtended at the metal center
by the coordinated ligands can allow framework flexing that results in a 300% change in lattice
volume. For the MIL system, these transitions are associated with removal/exchange of the
guest-species within the pores: For some other MOFs, guests can be removed/exchanged
without significant change to the framework structure.
Figure 2. For distortions of traditional solid-state framework materials (left), such as oxide-based perovskites, the
rotation of an individual octahedral unit is correlated to rotations of other corner-sharing octahedra throughout the
structure. By contrast, the expanded molecular nature of MOFs can allow for a greater range of distortions (right). This
allows for a large variety of potential polymorphs, and pronounced framework flexibility, such as seen for MIL-53 which
undergoes a B-style distortion upon guest removal.
MOFs are typically prepared in solution of the metal salt and organic ligand where the solvents
are typically pure/mixtures of small molecule alcohols, water, and dimethyl formamide. They
form through a process of self-assembly, with the labile coordination bonds able to form and
break dynamically as the framework assembles (with the possibility of healing defects during
272
synthesis). The as-prepared frameworks most typically have molecules from the solvent used for
synthesis contained within the pores. For some MOFs, these molecules can be removed
thermally and or under vacuum (or in some cases exchanged then removed), without collapsing
the framework structure, to leave a vacant framework and open pore structure.
Functional properties and applications of MOFs
MOFs have widely varied functional properties with valuable potential applications spanning
energy storage and carbon dioxide capture to molecular sensing and switching to catalysis and
energy conversion. These functional properties are derived from the MOF framework (and pore)
geometry, as well as non-innocent components within the framework, for example, chemically-,
magnetically-, electronically-, or optically-active centers.
Porosity is perhaps the most widespread MOF characteristic, from which a large part of their
functional behavior is derived. The nan-scale pores in the framework, which contains noncoordinated "guest" molecules in the as-synthesized material (typically the solvent used in the
framework synthesis) can be evacuated at elevated temperatures or under reduced pressures to
leave a "desolvated" framework. In many cases, the framework porosity is retained upon
desolvation to provide an extensive vacant pore network with high internal surface area. This
vacant host can subsequently be useful for guest storage (possibly with specific binding sites on
the pore surface to enhance host-guest interaction and, accordingly, heats of sorption), size-,
shape-, and enantio-selective separations (based on pore geometry), chemically-selective
separations (based on different relative sorption affinities), and selective catalysis at active sites.
Due to their robust porosity and reversible guest-exchange behavior, MOFs are often compared
to zeolites with potential applications in related areas. Indeed, the diverse range of known MOF
topologies include structural analogues of zeolites, based on imidazolate-rather than oxidebridging of tetrahedral units. Compared to zeolites, these MOFs can have close to one order of
magnitude higher surface area and higher guest uptake capacity, but typically lower thermal and
chemical stabilities.
The functional behavior of active (chemical, magnetic, electronic, optical) centers, both metal
and ligand-based, is often retained upon incorporation into a MOF to produce chemically-,
magnetically-, electronically-, or optically-functionalized MOFs. The physical linking of these
active components to form the MOF framework can generate new functionality through the
potentially enhanced communication and cooperativity between active centers, for example, to
provide new magnetic exchange pathways. Furthermore, in porous systems there is potential for
interplay between the porosity and the active functionality, resulting in guest-dependent
functionality with additional prospective applications of such multifunctional MOFs in
molecular sensing, etc. For example, in porous frameworks incorporating spin-crossover centers,
guest-dependent spin-state switching has been documented.
Finally, the intrinsic topology and flexibility of the framework can itself impart functionality. For
example, negative thermal expansion behaviora reduction in volume upon heatingcan arise
273
from thermal-population low energy vibrational modes (i.e., dynamic distortions) that induce a
contraction of the lattice. This behavior, recently recognized in expanded MOFs and cyanidebridged framework materials, has potential applications in athermalizing material dimensions
for high precision applications.
Metal organic frameworks under pressure
With even subtle changes in MOF structure often producing disproportionally large changes in
functional behavior, pressure can significantly influence MOF functionalities. Hence,
understanding the pressure dependence of MOFs and how this couples to their functional
properties is not only of fundamental interest, but is relevant to the development of MOF-based
technologies.
For example, an important consideration for applications of porous MOFs in gas storage is
optimizing not only the gravimetric capacity but also the volumetric capacity. Dispersed or
powdered materials typically occupy <50% of a container volume and, as such, compression of
MOF powders to form pellets etc. that maximize sample packing densities and, hence,
volumetric capacities is advantageous. Any changes to the framework and pore dimensions that
might occur under pressure would impact sorption behavior, including sorption selectivity, total
capacity and access to binding sites.
Due to their low density, often porous, structures, MOFs are disposed to be highly compressible,
exhibiting considerable sensitivity of the structure to applied pressure. Transitions occur at low
pressures compared to conventional solid-state materials. Moreover, their numerous structural
degrees of freedom are likely to be associated with a rich variety of structural distortions
including flexing, displacive phase transitions, shifting of independent interpenetrated networks,
and amorphization. Further chemical reactions and bond rearrangements can be induced under
pressure, to not only change the MOF structure but the framework topology. Electronic,
magnetic and optical functionalities are typically extremely sensitive to the electronic and atomic
structure and their well-recognized intrinsic pressure-dependence is mirrored in electronically-,
magnetically- or optically-functionalized MOFs.
The pore network within the MOF can be as important as the MOF framework structure itself,
in determining the behavior observed under pressure. The small molecule fluids often used to
transmit pressure uniformly to a solid MOF sample (e.g. methanol, ethanol, water) can be readily
accommodated within the MOF pores. Under pressure, the contents/chemistry of the pores can
change, due to insertion of molecules from the fluid surrounding the MOF, thereby impacting
the framework response. Both compression behavior and structural transitions can be
influenced. Accordingly, 3 phases are relevant to the high pressure behavior of MOFs: the
MOF lattice itself, the pore space within the MOF, and the fluid media surrounding the MOF.
Compression behavior
The low density, flexible MOF structures are generally soft and compressible compared to other
solid state materials. To date, bulk moduli (K) in the range 6-30 GPa-1 have been documented in
274
MOFs. (Higher apparent bulk moduli have been observed, however, as these are associated with
guest-uptake and changes in chemistry, these values are not a true representation of the MOF
compressibility).
At the upper limit, a bulk modulus of 30 GPa-1 is comparable to soft ionic salts such as sodium
chloride. This was observed for HKUST-1,1 which is amongst the least flexible MOFs studied to
date, being constructed from inflexible components (e.g. the aromatic ligand) and due to the
architecturally robust topology (based on triangular connections/shapes).
At the lower extreme, soft MOFs with bulk moduli of 6 GPa-1 are as compressible as polymeric
materials. These include the zeolitic imidazolate framework-8 (ZIF-8).2
Framework softening. A negative pressure dependence of the bulk modulus (K)
Normally materials become stiffer and more difficult to compress with increasing pressurethe
bulk modulus increases with increasing pressure. This positive pressure dependence of the bulk
modulus (K') reflects the increasing repulsion between atoms in dense phases as the atoms are
forced closer together.
The opposite behavior has been documented in MOFs, a negative pressure-dependence of the
bulk modulus.2, 3 (Only a handful studies of MOFs have been studied with sufficient precision to
evaluate the pressure-dependence of the bulk modulus). In low density MOFs, there is a lot of
open space within the material such that atoms are not necessarily forced into unfavorably close
contact with increasing pressure. Instead, the pressure can have the effect of distorting or flexing
the framework and framework connections. This may perturb the coordination bonding to
reduce the strength of the bonding interaction, enhance the bending flexibility of the
connections and, accordingly, lead to framework softening. Ultimately, a framework cannot
soften indefinitely and this softening instability leads to a structural phase transitions.
Figure 3. The zinc cyanide framework softens with increasing pressure.
275
Negative linear compressibility

Under uniform hydrostatic pressure materials are expected to shrink in every direction. In
MOFs, the coupling of structure distortions in multiple directions can give rise highly
anisotropic behavior. At the extreme, this can lead to an expansion along an individual direction,
while the overall volume is reduced under pressure. This phenomenon is referred to as negative
linear compressibility. A large negative linear compressibility effect has been documented in a
series of dicyanometallate-based frameworks materials4 and the high pressure phase of Zn(CN)2.5
For these systems, the negative compressibility's are an order of magnitude larger than for
traditional materials that show this behavior (e.g. elemental Se).
Guest- (i.e., fluid-) dependent compressibility
The first structural studies of a MOF system, at pressures greater than 0.01 GPa, focused on the
widely-studied Cu3(1,3,5-benzenetricarboxylate)3(H2O)3 (HKUST-1 or Cu-btc).1 Guestdependence of the compressibility demonstrated the potential for interaction of the pore
network with the small molecule fluidthe pressure-transmitting fluidwhich surround the
sample to ensure hydrostatic compression.
Specifically, for fluid molecules that are too large to enter the pores, an intrinsic, highly
compressibility is observed. In small molecule alcohol-based pressure-transmitting fluids, the
HKUST-1 framework exhibits a clear transition between two regions of near linear
compressibility: appearing "hard" at low pressure but becoming "soft" and compressing rapidly
beyond a threshold pressure (Figure 4). The transition is not accompanied by any change in
space group symmetry or notable variation in peak intensities. No such transition was apparent
without fluid. The compressibility transition pressure depends on the fluid and occurred at
lower pressure in iso-propanol (~0.8 GPa) compared to MEW (~2.2 GPa).
In the low pressure, "hard" regime progressive inclusion of extra guests underlies the reduced
compressibility. The increased pore occupancy raises the effective pressure exerted by guests,
reducing the difference between the internal and external forces on the framework and, thereby,
mitigating the effect of increasing applied pressure. Compressibility in the 'hard' regime, where
additional guests are forced into the framework, was independent of the guest and appears to be
intrinsic to the framework. This was first documented using powder diffraction1 and
subsequently confirmed using single crystal diffraction.6
The abrupt increase in compressibility at higher pressures is attributed to a reduced rate of guest
inclusion. In the 'soft' regime, where the framework and any contained guests compress together
without changes to the system composition, the compressibility seems remarkably tolerant to
the quantity/type of guest. This suggests that the contained guests offer little resistance to the
compression of the surrounding framework, which is consistent with the low bulk moduli of the
neat fluids (K~1-2 GPa).
276
Figure 4. HKUST-1 shows pressure-induced guest-sorption which impacts the apparent compressibility by changing the
"pressure" within the MOF pores. For fluid molecules that are too large to enter the pores, the intrinsic compression
behavior of the MOF is observed.1
Pressure-induced transitions
Structure transitions: Crystalline or amorphous? Reversible? Intrinsic or guest-dependent?

Porous phases, such as MOFs, are meta-stable relative to dense polymorphs of the same
composition. Calorimetric studies show that for a given composition, the enthalpy of formation
is generally correlated with the molar volumestructures with lower density are energetically
less stable. Transformation to less/non-porous phases (either crystalline or amorphous) are
therefore expected when an appropriate driving force, such as applied pressure, is provided.
Such transformations will not always be reversed upon release of pressure.
Due to the structural flexibility of MOFs, phase transitions are observed at low pressure ranges
(i.e., 0-10 GPa) compared to conventional solids. Both crystalline-to-crystalline phase transitions
and crystalline-to-amorphous phase transitions are observed. Transitions can be reversible or
irreversible. While the majority of transitions are displacive, some involve changes in the
coordination bonding.
Fluid-dependent transitions
The fluid media used to transmit pressure hydrostatically to the MOF can influence the
structural transitions observed. Where the molecules in the fluid are too large to enter the pores,
the intrinsic phase behavior (i.e. not involving a change in the MOF/pore chemistry) occurs. For
small molecule fluids that can enter the MOF pores under pressure, forcing extra molecules into
the pores under pressure can induce different transitions. For certain systems, fluid molecules
introduced under pressure can displace small ligands coordinated to the metal ion nodes within
the framework.
For example, the intrinsic high pressure behavior of ZIF-8 framework involves an irreversible
transition to an amorphous phase at 0.34 GPaan order of magnitude lower pressure than
amorphization transitions are observed in the less expanded zeolite with the same topology.2 In
277
small molecule methanol-ethanol fluid, additional guests are forced into the pores as the
pressure is increased. Beyond 1.5 GPa, a structural transition occurs involving twisting of the
bridging ligands in the framework to increase the size/volume of pores within the MOF.7
Surprisingly, even for framework materials without guest-accessible porosity at ambient
conditions, the fluid media influence the high pressure behavior.5 In zinc cyanide, the doubly
interpenetrated pristine material is not porous. However, this material can undergo a number of
different transitions depending on the fluid media. Remarkably, for small molecule fluids, the
framework can undergo a reconstructive transition to several different non-interpenetrated
porous phasesincreasing the crystal volume, under pressure, by a factor of 2! The topology of
the new non-interpenetrated framework formed depends on the fluid medium used. Molecules
from the fluid are included in the pores of these non-interpenetrated phases. While the volume
of the crystal increases under pressure, the overall system volume (the solid+fluid in the DAC) is
reduced. The phases are meta-stable, and can be recovered at ambient pressure.
Figure 5. Despite the zinc cyanide framework material being non-porous at ambient pressure, under pressure it can
transition to different phases depending on the fluid media. The intrinsic transition, in large molecule fluids involves a
simple distortion. In small molecule fluids, the framework undergoes a reconstructive transition to less dense, porous
phases.5
Metal-based transitions. Electronic & spin state switching

Functional behavior of active metal centers incorporated into MOF can be influenced by
pressure. For example, a re-orientation of the Jahn-Teller axis has been observed in a
magnetically-ordered MOF material, CuF2(H2O)2(pyrazine) with this re-orientation changing
the type of magnetic ordering.8 At ambient pressures, CuF2(H2O)2(pyrazine) exhibits 2-D antiferromagnetic ordering via a strong network of O-HF H-bonds that bridge linear Cu-pyrazine
chains into a pseudo-3-D network. Structural studies as a function of pressure revealed a
sequential re-orientation of the Jahn-Teller-like axis, which is orthogonal to the magneticordering plane in the ambient pressure system (Figure 5). Complementary high pressure SQUID
magnetometry measurements showed a transition from 2-D to 1-D ordering at ~0.8 GPa,
consistent with the re-orientation of the magnetic orbital (dx2 y2) from the H-bonding plane
278
(Phase-I) to along the Cu-pyrazine chains (Phase-II). This demonstrates the strong pressuredependence of magnetic behavior.
Figure 5. High pressure diffraction studies of CuF2(H2O)2(pyrazine) reveal abrupt changes in the lattice parameters
corresponding to the sequential reorientation of the elongated Jahn-Teller-like axis. This is reflected by change in the
magnetic ordering.8
Practical considerations
As detailed earlier, the choice of fluid pressure transmitting fluid can significantly impact the
compressibility and transitions observed in framework materials under pressure due to the
potential for molecules from the fluid to enter the pores of the framework. Whether a fluid
penetrates depends on the size of the pores. Typically large molecule silicon oils and fluorinerts
have been used as non-penetrating media to reveal the intrinsic pressure behavior of the MOF.
The pressure-induced guest adsorption process can be slow relative to the change in pressure
for more rapid increases in pressure or for larger crystallites (where there as a longer path for the
guest molecules to traverse within the crystal) the guests may not completely penetrate the
whole crystal and a modified behavior can be observed.1
Where large changes in the crystallite geometry are induced under pressure, there must be
sufficient free space within the pressure cell to allow these macro scale changes to occur. In the
extreme case of zinc cyanide, where a transition from a doubly interpenetrated framework
structure to non-interpenetrated phases with half the density can occur, there must be sufficient
fluid space in the cell for the crystallites to double in volume, otherwise the transition is
suppressed.5
Conclusions
The structural versatility and flexibility of framework materials such as MOFs are associated
with rich variety of pressure-induced phenomena, occurring at much lower pressures than are
typical for solid-state materials. The often porous nature of these open framework materials
contributes additional complexity to their high pressure behavior. With the potential for guest
molecules to move between the pores defined by the framework and the surrounding
environment, an understanding their high pressure behavior most not only consider the
framework itself, but also the pore network and the media surrounding the framework. The low
279
pressure ranges at which transitions can be induced and their coupling to porosity opens unique
possibilities to manipulate the structure and properties of these emerging materials systems.
Acknowledgments
Use of the Advanced Photon Source, an Office of Science User Facility operated for the US
Department of Energy Office of Science by Argonne National Laboratory, was supported by the
US Department of Energy under Contract No. DE-AC0206CH11357.
References
1.
2.
3.
4.
Chapman KW, Halder GJ, Chupas PJ. Guest-dependent high pressure phenomena in a nanoporous
metal-organic framework material. J Am Chem Soc 130, 10524-10526 (2008).
Chapman KW, Halder GJ, Chupas PJ. Pressure-Induced Amorphization and Porosity Modification in
a MetalOrganic Framework. J Am Chem Soc 131, 17546-17547 (2009).
Chapman KW, Chupas PJ. Pressure enhancement of negative thermal expansion behavior and
induced framework softening in zinc cyanide. J Am Chem Soc 129, 10090-10091 (2007).
Cairns AB, Thompson AL, Tucker MG, Haines J, Goodwin AL. Rational Design of Materials with
Extreme Negative Compressibility: Selective Soft-Mode Frustration in KMn Ag(CN)2 (3). J Am Chem
Soc 134, 4454-4456 (2012).
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8.
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Lapidus SH, Halder GJ, Chupas PJ, Chapman KW. Exploiting High Pressures to Generate Porosity,
Polymorphism, And Lattice Expansion in the Nonporous Molecular Framework Zn(CN)2. J Am
Chem Soc 135, 7621-7628 (2013).
Graham AJ, Tan JC, Allan DR, Moggach SA. The effect of pressure on Cu-btc: framework
compression vs. guest inclusion. Chem Commun 48, 1535-1537 (2012).
Moggach SA, Bennett TD, Cheetham AK. The Effect of Pressure on ZIF-8: Increasing Pore Size with
Pressure and the Formation of a High-Pressure Phase at 1.47 GPa. Angew Chem, Int Ed Engl 48,
7087-7089 (2009).
Halder GJ, Chapman KW, Schlueter JA, Manson JL. Pressure-Induced Sequential Orbital
Reorientation in a Magnetic Framework Material. Angew Chem, Int Ed Engl 50, 419-421 (2011).
EosFit Demonstration and Workshop
EosFit
Demonstration
and
Ross
J. Angel,
Dipartimento
di Workshop
Geoscienze, Universit di Padova, Via G. Gradenigo 6, Padova,
35131, Italy.
Angel
email:
homepage:
www.rossangel.net
www.rossangel.net
Abstract
In this demonstration and workshop the EosFit suite of programs will be presented and used to
illustrate how P-V and P-V-T data can be analysed and fit with various types of Equations of
State in order to determine the bulk moduli and linear compressibilities of materials.
Keywords
Pressure, Volume, Bulk Modulus, EosFit, Equations of State

EosFit
pressure and temperature1. The ready availability of a variety of spread sheets and algebraic
software makes it relatively easy, in principle, to fit any EoS formulation to data. However, the
complex nature of some equation of state functions has led to their algebraic forms being misstated in the literature. The additional possibility of errors in coding the complex equations, and
the requirement to implement specific (non-standard) weighting methods to overcome
correlation problems, motivated us to provide not only a validated set of publicly-available selfconsistent validated algorithms for EoS calculations, but a software suite that makes EoS fitting
and calculations easy for a user. The EosFit suite of programs2 currently consists of four
components:
1. A set of subroutines for EoS calculations in the CrysFML library3 that can be used (in
the Fortran sense) by external programs. The entire library has been revalidated against
other software and against an ab-initio re-derivation of the EoS, which identified a
number of small errors in published formulae for some EoS.
2. A console program built on this library to perform EoS calculations and fitting for both
volume and linear isothermal data, isobaric data and P-T data. Linear data is handled by
cubing the quantities and treating them as volumes in all EoS formulations. Leastsquares fitting of EoS to data includes the option to weight the fit with the measurement
uncertainties in P, V and T simultaneously. The console program remains the research
and development platform. Recent additions to the console program include handling
of host-inclusion elasticity for isotropic systems4, simultaneous fitting of elastic and
volume data5, and Landau-type phase transitions6, 7.
281
3.
A full GUI program, specifically as an interactive data-analysis and teaching tool8 built
on the CrysFML library. For both applications, an immediate graphical presentation of
the results of a chosen analysis or fit is required, so the GUI includes all of the types of
plots required in EoS analysis of data.
4. A graphics dialog-based EosFit calculator that does simple P-V or P-V-T calculations.
Data and EoS parameters can be exchanged between all of the programs via text files of a
standard format. This allows, for example, a dataset to be evaluated and fit with an EoS in
EosFit-GUI, saved to an eos file, which then can be read into the calculator for rapid P-V-T
calculations, or read into Eosfit7c for more extensive thermodynamic calculations.
Availability
The CrysFML subroutine library, which includes the Eos module, is described at
http://www.ill.eu/other_sites/fullprof/php/programs.html, and can be downloaded from
https://forge.epn-campus.eu/projects/crysfml. Both the EosFit7c console program, the EosFitGUI and the EosFit-calculator programs are available for Windows, Linux and Mac operating
systems at www.rossangel.net, together with example datasets and complete documentation.
Acknowledgments
The development of EosFit was supported by ERC starting grant 307322 to Fabrizio Nestola of
the University of Padova, and by the Ministerio Espaol de Ciencia e Innovacin, Project
MAT2010-21270-C04-02, and MALTA Consolider CSD2007-0045 to Javier Gonzalez-Platas at
the University of La Laguna in Tenerife.
References
1.
2.
3.
Angel RJ. Pressure and Equations of State. In: Lecture Notes for the IUCr summer school, Erice
2016 (eds Fabbiani F, Parise J, Guthrie M) (2016).
Angel RJ, Gonzalez-Platas J, Alvaro M. EosFit7c and a Fortran module (library) for equation of
state calculations. Zeitschrift fr Kristallographie 229, 405-419 (2014).
Rodriguez-Carvajal J, Gonzalez-Platas J. Crystallographic Fortran 90 Modules Library (CrysFML):

a simple toolbox for crystallographic computing programs. IUCr Computing Commission
Newsletter 1, 50-58 (2003).
4.
5.
6.
7.
8.
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Angel RJ, Mazzucchelli ML, Alvaro M, Nimis P, Nestola F. Geobarometry from host-inclusion
systems: the role of elastic relaxation. American Mineralogist 99, 2146-2149 (2014).
Milani S, et al. Elastic behaviour of grossular garnet at high pressure and temperature. American
Mineralogist, submitted (2016).
Angel RJ, Alvaro M, Gonzalez-Platas J, Netsola F. A simple and general PVT Eos for structural
phase transitions, implemented in EosFit and applied to quartz. Contributions to Mineralogy and
Petrology, in prep (2016).
Angel RJ. High-Pressure Phase Transitions. In: Lecture Notes for the IUCr summer school, Erice
2016 (eds Fabbiani F, Parise J, Guthrie M) (2016).
Gonzalez-Platas J, Alvaro M, Angel RJ, Nestola F. EosFit7-GUI: A new GUI tool for equation of
state calculations and analyses. in preparation, (2016).
X-ray Intensity Data Reduction with ABSORB
X-rayJ.Intensity
Data Reduction
with ABSORB
Ross
Angel, Dipartimento
di Geoscienze,
Universit di Padova, Via G. Gradenigo 6, Padova,
35131, Italy.
Angel
email:
homepage:
www.rossangel.net
www.rossangel.net
Abstract
ABSORB is a program to calculate and apply absorption corrections to single-crystal X-ray

intensity data from any source, any detector type, and any instrument configuration.
Keywords
X-ray absorption, Intensity data, Diffraction, ABSORB

ABSORB
ABSORB was originally developed1 to correct single-crystal X-ray intensity data for absorption
only by crystals. The program was subsequently developed to handle data collected from crystals
held in various types of environmental devices including diamond-anvil pressure cells2.
ABSORB-7 is the current version3. It can be used for data collected with either an area detector
or a point detector from any type of diffractometer. It handles a variety of data file formats,
including SHELX hkl files and incommensurate data.
ABSORB-7 is configured so that it can be called from any external program. The description of
the crystal, instrument, and any environmental device along with instructions for data handling
are provided to the ABSORB program through a text file known as the experiment file. This file
consists of instructions and information specified by keywords that are completely documented
in the users manual. External programs, such as commercial diffractometer control or data
reduction programs can use ABSORB by creating this experiment file from user input and
running ABSORB directly. Crysalis-Pro4 uses ABSORB in this way.
ABSORB-GUI3 provides a simplified interface to ABSORB that guides the user through the
description of the more common experimental configurations for diffraction experiments. It can
import a lot of information directly from files generated by commercial diffractometer control
programs. ABSORB-GUI interacts with the main ABSORB program via text files in exactly the
same way in which other external programs do, but this interaction remains hidden unless the
user specifically wishes to manually edit the experiment file.
Availability
ABSORB-7 and ABSORB-GUI run under the Windows-2000, Windows-NT, Windows-XP and
Windows-7 operating systems. Both programs are available in a single installation package from
www.rossangel.net, which includes full documentation in a users manual, on-line help system,
283
and example files. A programmers guide is also provided to describe how to call and interact
with ABSORB-7 from other software.
Acknowledgments
Recent development of ABSORB-7 was supported by ERC starting grant 307322 to Fabrizio
Nestola of the University of Padova, and by the Ministerio Espaol de Ciencia e Innovacin,
Project MAT2010-21270-C04-02, and MALTA Consolider CSD2007-0045 to Javier GonzalezPlatas at the University of La Laguna in Tenerife.
References
1.
2.
3.
4.
284
Burnham CW. Computation of absorption corrections and the significance of end effects.
American Mineralogist 51, 159-167 (1966).
Angel RJ. Absorption corrections for diamond-anvil pressure cells implemented in a software
package Absorb-6.0. Journal of Applied Crystallography 37, 486-492 (2004).
Angel RJ, Gonzalez-Platas J. Absorb7 and Absorb-GUI for single-crystal absorption corrections.
Journal of Applied Crystallography 46, 252-254 (2013).

Rigaku Oxford Diffraction. Crysalis-Pro (2016).

(in chronological order of presentation)
285
286

Davide Comboni1, P. Lotti2, G.D. Gatta1, L. Pastero3
Dip. di Scienze della Terra, Univ. degli Studi di Milano, Milan, Italy
Elettra, Sincrotrone Trieste S.c.P.A., Trieste, Italy
3
Dip. di Scienze della Terra, Univ. degli studi di Torino, Turin, Italy
1
2
Aluminophosphate are objects of a growing research interest due

to their potential technological and industrial applications [e.g 1,2]. Their large
channels serve as ideal host for organic compounds and small polymers. Among
those, AlPO4-5 is a synthetic zeolite characterized by an open-framework of (P,Al)
O4 tetrahedra. The tetrahedra are connected to form six- and twelve-membered
rings, in such a way that a large channel (~7.3), parallel to the [001] direction,
occurs. Klap et al. [3] underlines that every crystal of AlPO4-5 is built up by three
different microdomains, in which the positions of the framework oxygen atoms
are slightly different; the main effect of the structural disorder is the very large
anisotropic displacement parameters of the framework oxygens. We performed
two in situ single-crystal synchrotron X-ray diffraction experiments using both
penetrating (methanol:ethanol:H2O mix, m:e:w) and non-penetrating (silicon oil)
pressure media [4]. The structure refinements showed that: 1) for compression in
m:e:w mix, H2O molecules are absorbed at low-P regime, forming a H2O-network
by H-bonding interaction; 2) the elastic parameters of the super-hydrated AlPO45 are different if compared to the one compressed in silicon oil; 3) the structural
deformation mechanisms of super-hydrated and regular AlPO4-5 are different; 4)
evidence of a incommensurately modulated structure occur (according to [3]), and
there is an evolution of the non-Bragg reflections with pressure.
The author acknowledges the Italian Ministry of Education, MIUR-Project:
Futuro in Ricerca 2012 - ImPACT- RBFR12CLQD.
[1] Tang Z.K. et al. Applied Physics Letters 1998; 73, 2287-2289; [2] Yang W.S.
et al. Microporous and mesoporous materials 2016; 219,87-92. [3] Klap G.J. et
al. Microporous and mesoporous materials 2000; 38, 403-412. [4] Gatta, G.D.
Microporous and Mesoporous Material 2010; 128, 7884.
Keywords: zeolites, AlPO4-5, high pressure.
287
Crystal structure of cubic arsenic(III) oxide and its helium

clathrate under pressure
Piotr A. Guka1, K.F. Dziubek2,3, A. Gadysiak3, M. Dranka1,
M. Hanfland4, A. Katrusiak3, J. Zachara1
Faculty of Chemistry, Warsaw Univ. of Technology, Warszawa, Poland

LENS, European Laboratory for Non-Linear Spectroscopy, Sesto Fiorentino,
Italy
3
Dept of Materials Chemistry, Faculty of Chemistry, Adam Mickiewicz Univ.,
1
2
Pozna, Poland
4
ESRF - The European Synchrotron, Grenoble, France
Crystal structure of arsenolite, the cubic polymorph of molecular arsenic(III)

oxide, has been determined up to 30 GPa. The bulk of the crystal is monotonically
compressed with no detectable anomalies to 60% of the initial volume at 30
GPa. The experimental As4O6 crystal compression exceeds that obtained by
various theoretical models within the DFT framework. The As4O6 molecules
are deformed toward more tetrahedral shape. Pressure above 3 GPa favors the
formation of As4O62He clathrate in the surface layer increasingly deeper with
pressure. Interestingly, this is the first example of helium clathrate formed in situ
with a solid molecular oxide and a proof that helium may permeate even nonporous single crystals in high-pressure (HP) diffraction studies. This indicates it is
an important and general phenomenon that needs to be taken into account when
doing HP diffraction studies in helium.
288
Crystal engineering of multicomponent constructs and the

impact of high pressure
Lauren Evelyn Connor1,2, G. Halbert1,2, I.D.H. Oswald1,2
Strathclyde Inst. of Pharmacy and Biomedical Sciences, Univ. of Strathclyde,

Glasgow, UK
2
EPSRC Centre for Continuous Manufacture and Crystallisation, Univ. of
Strathclyde, Glasgow, UK
1
Solid state modification such as cocrystallisation can improve the

physicochemical properties of the end multicomponent construct without altering
the chemical composition of the individual components. High pressure is known
to alter the thermodynamic stabilities of materials with the potential for isolating
materials that have not been observed before. This present study investigates
the challenging cocrystalline structure of the non-steroidal, anti-inflammatory
indomethacin with the sweetener component saccharin. Co-crystals, obtained
by slurry and solvent evaporative techniques, were chosen and compressed
to 6.33GPa using a Diamond Anvil Cell. Single crystal X-Ray diffraction
measurements show that the co-crystal remains in the same phase throughout
the compression with a triclinic, P-1 unit cell containing a busy 116 atoms with
plenty of void space to allow for compression in the originally 1143.93 volume
unit cell. The increase in pressure up to 6.33GPa leads to an overall compression
of the unit cell axes with a large decrease in the b-axis as compared to the c-axis.
The c-axis lies in the same direction as the main body of the indomethacin and
saccharin molecules making this axis fairly stable against compression. Diagonal
arrangements of the molecules within the unit cell allow for sheets of void space
to dissipate, contributing to the large decrease in the b-axis.
289
New mechanisms for negative linear compressibility in

molecular framework materials
Andrew B. Cairns1,2, A.L. Goodwin1, M. Mezouar2, J. Haines3
Inoragnic Chemistry Laboratory, Univ. of Oxford, Oxford, UK
3
Inst. Charles Gerhardt, Univ. Montpellier, Montpellier, France
1
2
Negative compressibility is a rare but desirable property

whereby a materials crystal structure actually expands in one (negative
linear compressibility, NLC) or two (negative area compressibility, NAC)
principal directions against application of increasing hydrostatic pressure. The
performance of such materialsfor use in, for e.g., sensitive interferometric or
ferroelectric pressure sensing devices, advanced actuators, or prototype artificial
musclecritically depends on the magnitude of intrinsic negative response. NLC
and NAC have been previously reported in a diverse range of materials: from the
elemental forms of selenium and tellurium, to transition metal oxides, halides
and chalcogenides [1], to more recent reports of NLC in molecular materials, and
metalorganic and metalcyanide frameworks [2].
In this poster I will explore, using examples from our work [3,4] as well as that
of others, how understanding known NLC and NAC materials can inform
material design, and how the versatile chemistry of molecular frameworks
the connecting of cationic metal nodes with anionic molecular linkers in one
or more dimensionsallows for the targeting, enhancing and coupling of
functionalities.Structural motifs identified point towards strategies for designing
the next-generation of these materials, including the simple wine-rack,
honeycomb and spring mechanisms, where hinging about nodes requires
volume reduction by simultaneous expansion and contraction in perpendicular
directions.
[1] R. Baughman, S. Stafstrom, C. Cui et al., Science, 1998, 279, 15221524
[2] A. B. Cairns et al., Phys. Chem. Chem. Phys., 2015, 17, 2044920465
[3] A. B. Cairns, J. Catafesta, C. Levelut, et al., Nature. Mater., 2013,12, 212216
[4] S. A. Hodgson, J. Adamson, S. J. Hunt, et al., Chem. Commun., 2014, 50, 5264
5268.
290
The evolution of interatomic and intermolecular interactions

and polymorphism of melamine at high pressure
Hannah Shelton1, P. Dera1, Y. Meng2, S. Tkachev3
Hawaii Inst. of Geophysics and Planetology, Univ. of Hawaii at Mnoa,

Honolulu, HI, USA
2
High Pressure Collaborative Access Team, Carnegie Inst. of Washington,
Advanced Photon Source, Argonne National Laboratory, IL, USA
3
Center for Advanced Radiation Sources, Univ. of Chicago, Argonne National
Laboratory, Chicago, IL, USA
1
Melamine (C3H6N6; 1,3,5-triazine-2,4,6-triamine) is an aromatic ring molecule,

with carbon and nitrogen atoms forming the ring body, and amine groups bonded
to each carbon. Melamine is widely used to produce laminate products, adhesives,
and flame retardants. However, melamine has a very similar structure to several
well known explosives, including triamino-trinitrobenzene (TATB). Additionally,
melamine may be a precursor in the synthesis of superhard carbon-nitrides, such
as -C3N4.In its solid form, individual melamine molecules are linked to others
via eight N-H hydrogen bonds. The superstructure of melamine forms corrugated
sheets of individual melamine molecules, where kinked planes of molecules are
stacked on top of one another. Several previous high pressure x-ray diffraction
and Raman spectroscopy studies have claimed that melamine undergoes two or
more phase transformation below 25 GPa. Our single crystal data demonstrate
that melamine retains the ambient, monoclinic structure up to almost 40 GPa. At
37 GPa, the unit cell volume has decreased by more than a factor of two without
significant chance in the molecular geometry, as the hydrogen bond distances
between molecular units decrease. A phase transition to a triclinic structure,
different than the one previously suggested, was found around 40 GPa. Examining
the effect hydrogen bonds have on melamines structure will allow it to be better
utilized as a chemical feedstock and analog for related compounds.
291
Density of carbonate melts along the CaCO3-MgCO3 join by

synchrotron X-ray radiography
Xenia Ritter1, C. Sanchez-Valle1, A. King2, N. Guignot2
1
2
Inst. fr Mineralogie, Universitt Mnster, Mnster,Germany

Synchrotron SOLEIL, Gif-sur-Yvette, France
The occurrence of carbonate-rich mantle rocks or diamonds in

kimberlites suggests that an important fraction of carbon is retained at depth [1].
Deep carbon has a huge impact on key role processes in the Earths interior such
as subduction, partial melting and volcanism [1]. Although the deep carbon cycle
has been investigated extensively, very little experimental data on the physical
properties of carbonate melts at relevant P-T conditions are available so far [2].
Among these physical properties, the density is of particular interest due to its
influence on percolation, ascent rate and buoyancy relations with surrounding
rocks.
Here we report in situ density measurements on carbonate liquids along the
CaCO3-MgCO3 join, including dolomite CaMg(CO3)2 and the eutectic composition
Ca66Mg33(CO3)2 at crustal and upper mantle conditions (<1.6 GPa, 2000K). The
density was measured by synchrotron X-ray radiography imaging at the beamline
Psich of Soleil in a Paris-Edinburgh press [3]. The measurements provide
preliminary constrains on the equation of state of carbonate liquids representative
for natural carbonatites, including compositions produced by the partial melting
of carbonated peridotites [1]. The results are compared with previous molecular
dynamics simulations and experimental data [4, 5, 6], and combined with density
data for silicate melts [7] and mantle minerals to discuss buoyancy relations in the
upper mantle and their evolutions with pressure. Finally, the implications of these
results for the ascent and migration of melts through the mantle are discussed.
[1] Dasgupta, R. and Hirschmann,M. M. 2010. EPSL 298, 1-13. [2] Jones, P. et al.
2013. Rev. Min. Geochem. 75, 289-322. [3] Nervo, L. et al. 2014. J. Appl. Cryst. 47,
1402-1416. [4] Liu, Q. et al. 2007. Contr. Mineral. Petrol. 153, 55-66. [5] Genge, M.
J. et al. 1995. EPSL 131, 225-238. [6] Vuilleumier, R. et al. 2014. GCA 141, 547-566.
[7] Malfait, W.J. et al. 2014. Nat. Geosci. 7, 122-125.
292
The best of both worlds; Combined X-ray and neutron studies

at high-pressure using lab source X-ray diffractometers and
laue neutron diffraction
Christopher H. Woodall1, J. Binns2, C.R. Ridley1, S. Parsons2,
K. Kamenev1, G. McIntyre3
School of Engineering and Centre for Science at Extreme Conditions, The
Univ. of Edinburgh, Edinburgh, UK
2
School of Chemistry and Centre for Science at Extreme Conditions, The
Univ. of Edinburgh, Edinburgh, UK
3
Bragg Inst., ANSTO, Lucas Heights, NSW, Australia
1
Neutron diffraction is an important tool in the study of light atomed systems

containing elements such as H, Li, Be and C. Such studies are often used to
complement simultaneous X-ray studies on the same material. Due to the
weakly interacting nature of neutrons and the weak sources of neutron radiation
available, however, often much larger sample volumes are required, typically,
orders of magnitude larger than equivalent X-ray experiments. The requirement
of large sample volume has limited the use of high-pressure neutron diffraction
in terms of maximum achievable pressures and data of sufficient quality for
quantitative solution and refinement of structural data.1,2
Previously the Paris-Edinburgh press has been the work horse of high-pressure
neutron diffraction work while developments elsewhere has seen diamond anvil
cell techniques developed and adapted in order to achieve pressures of up to
90 GPa with sample volumes equivalent to those used in high-pressure X-ray
diffraction experiments albeit with limits to the observable reciprocal space.3
Recently Binns et al. have suggested an alternative approach, adapting a standard
Merrill-Bassett design, typically associated with high-pressure X-ray work for
a combined X-ray and neutron diffraction study at high-pressure. Through the
use of a polychromatic beam and the Laue technique it is possible to perform
both single crystal neutron diffraction and X-ray diffraction on the same sample
loaded in the same cell ensuring consistency in the sample and the pressure it is
subjected to.
We report the first combined high-pressure X-ray and neutron diffraction study
of l-arginine. The data collected is from a single high-pressure loading of a single
crystal (~ 0.3 x 0.2 x 0.2 mm3) at pressures up to 1.5 GPa.
References
1
Guthrie, M. J. Phys.: Condens. Matter 2015, 27, 153201.
2
Binns, J. et al. IUCrJ 2016, 3.
3
Boehler, R. et al. High Pressure Research 2013, 33, 546.
293
Effects of irradiation-induced structural disordering in

zirconate pyrochlores at high pressures
Sulgiye Park1, C.L. Tracy1, F. Zhang2, C. Park3, C. Trautmann4,5,
S. Finkeldei6, M. Lang7, W.L. Mao1, R.C. Ewing1
Dept of Geological Sciences, Stanford Univ., Stanford, CA, USA

Dept of Nuclear Engineering, Univ. of Tennessee, Knoxville, TN, USA
3
Materials Science and Technology Division, Oak Ridge National Laboratory,
Oak Ridge, TN, USA
4
HPCAT, Carnegie Inst. of Washington, Argonne, IL, USA
5
GSI Helmholtzzentrum fr Schwerionenforschung, Darmstadt, Germany
6
Technische Univ. Darmstadt, Darmstadt, Germany
1
2
The effects of swift heavy ion irradiation-induced disordering on zirconate

compounds (A2Zr2O7where A = Sm, Er, Nd) at high pressures are investigated
using synchrotron X-ray diffraction (XRD). Irradiation experiments were
performed at the GSI Helmholtz Center with197Au ions accelerated to energy of
2.2 GeV. Angle dispersive synchrotron powder X-ray diffraction measurements
were completed at the Advanced Photon Source at Argonne National Laboratory,
where samples before and after irradiation were pressurized up to ~ 50 GPa
using diamond anvil cells. Analysis of the XRD data demonstrate that: 1)
Sm2Zr2O7and Nd2Zr2O7undergo a phase transformation from ordered pyrochlore
to a disordered defect-fluorite with swift heavy ion irradiation; 2) energetics of
disordering lower the pressure transition point in pyrochlores Sm2Zr2O7and
Nd2Zr2O7and; 3) swift heavy ion irradiation increases the pressure transition
point in a defect-fluorite Er2Zr2O7by introducing more interstitials. The effects of
disordering in different zirconate compositions under high pressure are explained
in terms of the variation in phase space with A-site cation substitution.
294
Unexpected high pressure and high temperature chemistry

in Xe-N2 mixtures
Dominique Laniel1, G. Weck1, P. Loubeyre1, S. de Panfilis2,
M. Santoro3, F. Gorelli3, O. Mathon4, G. Garbarino4,
M. Mezouar4
CEA, Arpajon, France

Univ. Roma La Sapienza, Dip. Fis., Rome, Italy
3
LENS, European Laboratory for Non-linear Spectroscopy and INFM, Sesto
Fiorentino, Florence, Italy
4
1
2
Recent numerical simulations predict xenon and nitrogen, two inert gases under
ambient conditions, to chemically react at high pressure to form a remarkable
covalently-bonded high energy density xenon nitride. In this study, we present a
thorough investigation of Xe-N2 mixtures to high pressures (184 GPa) and high
temperatures (2500 K). The Xe-N2 binary phase diagram was determined at
300 K from the pressure evolution of 14 different concentrations. The mixtures
properties were characterized using visual observations, Raman spectroscopy
as well as synchrotron X-ray diffraction and X-ray absorption spectroscopy
(XAS). Above 4.9 GPa, the Xe(N2)2 van der Waals compound was found stable,
adopting the MgCu2-type Laves phase structure (cubic, Fd-3m) with N2 molecules
spherically disordered. At 10 GPa, the cubic lattice undergoes a martensitic
phase transition into a tetragonal (I41/amd) unit cell, due to the growing N2
N2 quadrupole-quadrupole interaction inducing a partial ordering of the N2
molecules. No other phase transition was detected in Xe(N2)2 up to 184 GPa, even
when heating the sample to 2500 K. Its great stability is explained by an intriguing
bondless redistribution of electronic density between N2-N2 and Xe-N2 entities.
However, for Xe-N2 mixtures in excess of nitrogen with respect to Xe(N2)2, a
novel compound was produced above 1500 K and 140 GPa along with Xe(N2)2.
Previously unobserved low frequency Raman modes and XAS measurements
suggest the new compound to be a Xe-N covalently-bonded solid. Surprisingly,
this xenon nitride does not correspond to the predicted XeN6, but instead seems
to be of even greater nitrogen concentration.
295
Laser annealing after a kinetically hindered phase transition

in the pyrochlore La2Sn2O7: A method for true structure
determination and a pathway to recovery
Christian Childs1, S. Petitigirard2, A.L. Hector3, C.J. Pickard4,
J. Smith5, A. Salamat1
Dept of Physics and Astronomy and HiPSEC,Univ. of Nevada Las Vegas,

Las Vegas, NV, USA
2
Bayerisches GeoInstitut (BGI), Univ. of Bayreuth, Bayreuth, Germany
3
Chemistry, Univ. of Southampton, Southampton, UK
4
Dept of Materials Science & Metallurgy, Univ. of Cambridge, Cambridge, UK
5
High Pressure Collaborating Access Team at Advanced Photon Source, Geophysical Laboratory,
Carnegie Institution of Washington, Argonne, IL, USA
1
There is significant interest in identifying novel materials for use in radioactive

waste applications and studying their structural properties. Previous research
has shown that pyrochlore compounds might be promising candidates
for such purposes. In an attempt to obtain a broader understanding of the
structural stability of these compounds, we have investigated the pyrochlore
La2Sn2O7under extreme conditions: high temperature isobaric and high-pressure
isothermal study. Both quasi-hydrostatic and non-hydrostatic isothermal high
pressure compression runs were undertaken to reveal alternative structural
transformations and studied using synchrotron angle-dispersive X-ray diffraction
and Raman scattering techniques. Compression using He as a quasi-hydrostatic
pressure transmitting medium permitted the observation of a new high pressure
phase via a kinetically hindered first-order phase transition that begins at 49
GPa and finally goes to completion at 61 GPa. Alternatively, the non-hydrostatic
compression, using no pressure-transmitting medium, revealed the emergence
of a phase transition at 46 GPa. However, it appears that this process occurs
via a stress-induced pathway and in fact transforms into an amorphized phase
by 67 GPa. Annealing the amorphized phase, through laser heating, at 70GPa
allows us to crystallize the high pressure phase which is recoverable to ambient
conditions. We have performed ab-initio random structure searching (AIRSS) to
compare to our x-ray diffraction results.
296
Distinct mechanical response of brittle, plastic and elastic

single crystals studied by nanoindentation technique
Ramesh Devarapalli1, S. Kadambi2, R. Upadrasta2, C.M. Reddy1
Dept of Chemical Sciences, Indian Inst. of Science Education and Research

(IISER), Kolkata, India
2
Dept ofMaterials Engineering, Indian Inst. of Science (IISc), Bangalore,
India
1
Here in this study, we synthesized elastically bendable single crystals of

a n-type semiconducting naphthalene derivative, N,N-diethyl-1,4,5,8naphthalenetetracarboxylic diimide and propose its structure based bending
mechanism. In addition, we also evaluated its nano-mechanical properties and
mechanical flexibility by using nanoindentation technique and compared with
two other NDI derivatives, N,N-dimethyl-1,4,5,8-naphthalenetetracarboxylic
diimide and N,N-din-propyl-1,4,5,8-naphthalenetetracarboxylic diimide that
show drastically different mechanical behavior, i.e. plastic andbrittle nature,
respectively. These NDIs, with rigidly planar and high conjugated aromatic
core groups, have attracted considerable recent interest for fabrication of soft
electronic devices, conducting thin films and molecular sensors. The NDI
derivatives are finding use in a range of biomimetic and bioinspired artificial
systems including electron and energy transfer systems due to their attractive
photophysical properties. Here, we carried out detailed mechanical deformation
studies for the first time on all the three types, plastic, elastic and brittle, crystals
by bending tests using nanoindentation technique to unravel their distinct
mechanical response. Hence the study has implications for understanding
mechanical flexibility of semiconducting organic crystals.
297
Comparative HP/HT elasticity measurements on singlecrystals of hydrous/iron-bearing ringwoodite

Kirsten Schulze1, H. Marquardt1, T. Kawazoe1, A. Kurnosov1,
M. Koch-Mller2, T. Boffa Ballaran1
1
2
Bayerisches Geoinstitut, Univ. Bayreuth, Bayreuth, Germany

Deutsches Geoforschungszentrum (GFZ), Potsdam, Germany
Olivine and its high-pressure polymorphs wadsleyite and ringwoodite are the
most abundant minerals in the upper mantle. The elastic tensor of ringwoodite
is not only dependent on the pressure and temperature conditions but also
on the Fe/Mg ratio and the hydration state. Differences in experimental set
up and sample characterisation between published studies make it difficult to
reliably quantify the effect of these chemical variations. We present first results
of internally consistent single-crystal elasticity measurements of chemically
diverse ringwoodite crystals at high pressure. Single-crystals of ringwoodite were
synthesised in multi-anvil experiments with chemical compositions ranging from
Mg2SiO4 to (Mg0.89,Fe0.11)2SiO4 and about 0.4 wt.%H20 to more than 2 wt.%H20.
Four ringwoodite single-crystals with different compositions were oriented,
double-side polished and cut into quarter-circles with a FEI Scios Focused Ion
Beam (FIB). To ensure the same temperature and pressure conditions for all
samples, all four samples were loaded in the pressure chamber of one diamond
anvil cell (DAC), ruby spheres were added as a pressure marker. We perform
single-crystal x-ray diffraction (XRD) and Brillouin spectroscopy measurements
to determine the effect of Fe and OH-defects on the elastic constants and
densities at high pressure. XRD at 1 GPa showed that the incorporation of OHdefects equivalent to ~1.8 wt.%H2O in Fo90 ringwoodite leads to an increase
in the unit cell volume of ~ 2.8 3. A decrease in unit cell volume of ~ 3 3 is
observed in Mg-endmember ringwoodite compared to a Fo90 ringwoodite with
similar water content. Brillouin spectroscopy at 1 GPa shows decreased phonon
frequency shifts with increasing hydration in Fo90 ringwoodite and highest
frequency shifts in the Mg-endmember.
298
Poster Abstracts
in alphabetical order
(presenting authors are shown underlined)
299
300
The study of the effects of high-energy electrons to the

structure of nanoparticle silicon carbide
Bekhzodjon Abdurakhimov,M.Y. Tashmetov
Inst. of Nuclear Physics, Tashkent, Uzbekistan
The effect of 3-5 MeV energy electron beam to structural

parameters of silicon carbide nanoparticles have been studied.
POSTER 1
Nano-size (56 nm) silicon carbide powder, which is taken as
a sample is irradiated at the Electronics U-003 linear accelerator. Structure
of samples, which were unirradiated and irradiated at various doses have been
implemented at the X-ray diffractometer. At the experiment, there is used U = 40
kV voltage and I = 30 mA current strength at the copper anode diffractometer
tube. Obtained results is full profile processed at the FullProf program by using
Rietveld method. Calculations are carried out to determine structural shape of
the sample based on the powder samples data of space groups P63mc, P3ml, P3m
and F43m. F43m space group elementary cell, which is proposed via obtained
result of research is determined as a smallest difference in the cubic structural
model. To determine full width at half maximum (FWHM) of the reflex (220) and
to find its high accuracy value calculations have been performed with MATLAB
program and it was defined that the decrease of the value FWHM within
increasing absorption dose.
It can be predicted that the decline of the value FWHM causes to grow the
size of nanoparticle in the sample. Because the size of nanoparticle is inverse
proportional to the FWHM according to Debye-Scherrer equation. The size of
unirradiated and irradiated nanoparticles under absorption doses 50, 100, 150
kGr is determined by using of Debye-Scherrer equation. Defined that the increase
of irradiation dose causes to grow the size of nanoparticles.
301
Mineral inclusions in natural diamonds: the high-pressure

behaviour of CaSiO3with walstromite-like crystal structure
Chiara Anzolini1, F. Nestola1, M. Merlini2, M. Hanfland3,
S. Milani1, R.J. Angel1
Dept of Geosciences, Univ. of Padua, Padova, Italy

Dept of Earth Sciences Ardito Desio, Univ. of Milan, Milano, Italy
3
ESRF, European Synchrotron Radiation Facility, Grenoble,France
1
2
POSTER 2
Triclinic CaSiO3 with walstromite-like structure is the dominant

Ca-bearing phase in super-deep diamonds [1]. Such mineral is crucial to our
understanding of the physical and chemical characteristics of the very deep
Earth as it is considered the product of back-transformation from CaSiO3perovskite, which is stable at lower mantle pressure and temperature conditions.
Nevertheless, at the present day there are no reliable literature data on the
pressure at which CaSiO3 crystallizes within diamonds and therefore no valid
evidence for CaSiO3-walstromite to derive from CaSiO3-perovskite. A method
recently improved by Angel et al. [2] would allow us to estimate the entrapment
pressure of an inclusion within the diamond by knowing its residual pressure,
measured at ambient conditions, and the thermoelastic parameters of the mineral
inclusion and the diamond host.
Here for the first time we have determined the in situ high-pressure behaviour
of CaSiO3 with walstromite-like structure by single-crystal X-ray diffraction
using synchrotron radiation at European Synchrotron Radiation Facility ID09
beamline (Grenoble, France). The crystal structure and the unit-cell parameters
were measured up to about 8 GPa. This allowed us not only to determine its static
bulk modulus and its first pressure derivative, but also to evaluate the degree of
anisotropy under compression. Finally, our results were compared with the highpressure data on CaSiO3-wollastonite and CaSiO3-perovskite, providing a wide
scenario about the high-pressure behaviour of CaSiO3-walstromite.
This work is supported by Fondazione Cassa di Risparmio di Padova e Rovigo and

by the project INDIMEDEA, funded by the ERC Starting Grant 2012 to Fabrizio
Nestola (agreement N 307322).
[1] Joswig et al (1999) EPSL 173,1-6.

[2] Angel et al. (2015) Russ Geol Geophys 56, 211-220.
302
The effect of pressure on the anti-epileptic Levetiracetam

Suse S. Bebiano1, T. Leyssens2, J.H. Ter Horst1, I.D.H. Oswald1
EPSRC Centre for Innovative Manufacturing in Continuous

Manufacturing and Crystallisation (CMAC), Strathclyde Inst.
of Pharmacy and Biomedical Sciences (SIPBS), Technology and
Innovation Centre,Univ. of Strathclyde, Glasgow, UK
2
Inst. of Condensed Matter and Nanosciences,Univ. Catholique de
Louvain, Louvain-la-Neuve,Belgium
1
POSTER 3
In the pharmaceutical industry, the knowledge on the crystallization and solid

state of active pharmaceutical ingredient (API) is an important step in the
manufacturing. APIs can often crystallize into different crystal forms such as
polymorphs of pure compound, solvates, salts or co-crystals. These forms could
present different physicochemical properties (e.g., solubility, bioavailability,
dissolution rate), that could affect the performance of the API in the secondary
processing (e.g., tabletting), during their storage in their final form and in the
biological system upon administration. Conversion of crystal forms could occur
during these stages. Therefore, it is of utmost importance to understand solid
phase behaviour and be aware of solid form issues of particular systems.
Levetiracetam, the S-enantiomer of the chiral 2-(2-oxopyrrolidin-1-yl)
butanamide, is a nootropic drug used as anticonvulsant in the treatment of
epilepsy. Levetiracetam has only one known crystalline form. Etiracetam is the
racemic compound constructed of both enantiomers and two polymorphic forms
and one hydrate are reported for this compound.
In this work we investigated the effect of high-pressure on levetiracetam and
etiracetam using a diamond anvil cell. For levetiracetam a possible modification of
crystal structure was observed by Raman spectroscopy upon applying a pressure
of 1.50 GPa. At this pressure the peaks in the spectrum at low-wavenumber
region, < 200 cm-1, showed a substantial shift to higher frequencies. In addition,
a different morphology was observed at increased pressure.Single x-ray diffraction
(SXRD) was carried out to confirm the crystal structure change for levetiracetam.
Future work will include the study of etiracetam. Also, mixtures of both
compounds will be investigated to see the shift in the eutectic point in the binary
system of both enantiomers.
303
Linking crystal structure to composition in tourmaline:

a multi-method investigation of synthetic dravite,
maruyamaite, magnesio-foitite, and oxy-uvite
Eleanor Berryman1,2, B. Wunder2, A. Ertl3,4, M. Koch-Mller2, D.
Rhede2, K. Scheidl4, G. Giester4, W. Heinrich2
Fachgebiet Mineralogie-Petrologie, Technische Univ. Berlin, Berlin,

Germany
2
GFZ German Research Centre for Geosciences, Potsdam, Germany
3
Mineralogisch-Petrographische Abt., Naturhistorisches Museum, Vienna,
1
POSTER 4
Austria
4
Inst. fr Mineralogie und Kristallographie, Geozentrum, Univ. Wien, Vienna, Austria
The crystal structures of synthetic K-dravite, dravite, oxy-uvite, and magnesiofoitite are investigated by polarized Raman spectroscopy, SREF and powder-XRD
to understand how the X-site composition influences tourmalines short- and
long-range structure. The use of compositionally simple tourmalines facilitates the
determination of site occupancy in the SREF and band assignment in the Raman
spectra. Mg-Al disorder between the Y and Z sites is constrained in the SREF
and from the relative integrated peak intensities of the Raman bands in the O-H
stretching vibrational range (32503850 cm-1). The unit cell volume of tourmaline
increases from magnesio-foitite (1558.4(3) 3) to dravite (1569.5(4)-1571.7(3) 3)
to oxy-uvite (1572.4(2) 3) to K-dravite (1588.1(2) 3), mainly by lengthening of
the c axis. Increasing the size of the X-site from dravite (Na) to K-dravite (K)
is accommodated locally in the crystal structure, resulting in the shortening
of the neighbouring O1-H1 bond. In oxy-uvite, Ca2+ is locally associated with a
deprotonated W (O1) site, whereas vacant X sites are neighboured by protonated
W (O1) sites. Increasing the size of the X-site-occupying ion does not detectably
affect bonding between the other sites, however the higher charge of Ca and the
deprotonated W (O1) site in oxy-uvite are correlated to changes in the lattice
vibration Raman spectrum (1001200 cm-1), particularly for bands assigned to
the T6O18 ring. The Raman spectrum of magnesio-foitite deviates from those of
K-dravite, dravite, and oxy-uvite in both the lattice and O-H stretching vibrational
ranges. The vacant X site is correlated with long- and short-range changes in the
crystal structure, i.e., deformation of the T6O18 ring and lengthening of the O1-H1
and O3-H3 bonds. However, X-site vacancies in K-dravite, dravite, and oxy-uvite
result only in the lengthening of the neighboring O1-H1 bond and do not result in
identifiable changes in the lattice-bonding environment.
304
Trace element distribution between Earth mantle phases and

carbonates at HP/HT
Nicole Biedermann1, M. Wilke2, K. Appel1
1
2
European XFEL, Hamburg, Germany

Univ. of Potsdam, Dept of Geosciences, Potsdam-Golm, Germany
Carbonates are key-phases in the chemistry and dynamics of

POSTER 5
our planet. They are present from marine environments down to
the lower mantle. Carbonate inclusions in kimberlitic diamonds
have been shown to carry significant amounts of Sr and REE (Brenker et al., 2005;
2007). Carbonate-related element transport processes to the deep regions of the
Earth and back are still not well understood. In addition, very little is known
about trace element distribution between carbonates and other mantle phases.
We want to study reactions between Sr and REE-containing carbonates with
relevant mantle phases (olivine and perovskite) using XRD for structural and XRF
for chemical analysis.
Status quo
We synthesized carbonate minerals in the system to be studied and characterized
them. We investigated the structural dependence of SrCO3 with pressure by
Raman spectroscopy and could observe a phase transition to a post SrCO3 II
phase at 26 GPa. This knowledge allows us to tune the relevant P-T-conditions
of interest and to learn about the structural dependence of the trace element
partitioning.
Work of interest
We will measure the chemical changes of the mantle phases olivine, its HP/HT
polymorphs wadsleyite and ringwoodite, and perovskite in equilibrium with Sr
and REE-holding carbonates. Conditions of the upper and lower mantle of the
Earth (T up to 2000C, P up to 60 GPa) will be achieved in laser-heated diamond
anvil cells (LH-DAC) and XRF/XRD measurements are planned to be performed
in combination with synchrotron radiation. We plan to place carbonate and
silicate samples in the DAC sample chamber and to laser-heat the overlapping
region between carbonate and silicate minerals. This dataset will provide unique
information on the fractionation of REE and Sr between carbonates and mantle
phases for conditions in the upper and lower mantle.
References
[1] Brenker et al. 2005, Earth and Planetary Science Letters, 236, 579.
[2] Brenker et al. 2007, Earth and Planetary Science Letters, 260, 1.
305
Operando diffraction techniques for understanding the

synthesis, structure and function of advanced materials
William R. Brant,T. Gustafsson, K. Edstrm
Dept of Chemistry, ngstrm Laboratory,Uppsala Univ., Uppsala, Sweden
Operando diffraction is an extremely powerful technique for

investigating reaction mechanisms in battery materials. To date,
POSTER 6
the vast majority of these experiments have been performed
using synchrotron X-ray diffraction, predominantly due to the fast data collection
times possible. However, operando neutron diffraction experiments are becoming
increasingly popular due to a range of new cell designs increasing the accessibility
of the technique [1], [2], and operando X-ray diffraction experiments can be
readily performed on a laboratory diffractometer with an appropriate set up. To
further expand the use of operando neutron diffraction we have modified a coin
type cell to obtain a balance between reasonable electrochemical cycling rates
and high quality diffraction. The modified cells contain a large quantity of active
material (~300-400 mg) to a much smaller amount of electrolyte (~1050 L),
separator and lithium metal. The smaller volume of electrolyte is particularly
vital as it substantially reduces the cost of the experiment, as deuteration may
no longer be necessary. In house operando X-ray diffraction, on the other hand,
has been used to follow the phase transformation behavior of LiFeSO4F to the
intermediate, Li0.5FeSO4F [3], and end member, FeSO4F, during electrochemical
cycling. A pouch cell was cycled at the rates C/2, C/5 and C/50 and diffraction
patterns were collected over the 2 range 17-36 for 3, 10 and 20 min per pattern
respectively. Using these operando diffraction conditions the formation of the
intermediate phase was tracked as a function of rate and electrode thickness.
Thus, this contribution will focus on progress that is being made on performing
fast operando style diffraction experiments using these two less conventional
approaches.
[1] M. Bianchini et al., J. Phys. Chem. C, 2014, 118, 25947. [2] R. Petibon et al.,
Electrochim. Acta, 2015, 174, 417. [3] A. Sobkowiak et al., Chem. Mater., 2014, 26,
462.
306
New mechanisms for negative linear compressibility in

molecular framework materials
Andrew B. Cairns1,2, A.L. Goodwin1, M. Mezouar2, J. Haines3
Inoragnic Chemistry Laboratory, Univ. of Oxford, Oxford, UK
3
Inst. Charles Gerhardt, Univ. Montpellier, Montpellier, France
1
2
POSTER 7
Negative compressibility is a rare but desirable property

whereby a materials crystal structure actually expands in one
(negative linear compressibility, NLC) or two (negative area compressibility, NAC)
principal directions against application of increasing hydrostatic pressure. The
performance of such materialsfor use in, for e.g., sensitive interferometric or
ferroelectric pressure sensing devices, advanced actuators, or prototype artificial
musclecritically depends on the magnitude of intrinsic negative response. NLC
and NAC have been previously reported in a diverse range of materials: from the
elemental forms of selenium and tellurium, to transition metal oxides, halides
and chalcogenides [1], to more recent reports of NLC in molecular materials, and
metalorganic and metalcyanide frameworks [2].
In this poster I will explore, using examples from our work [3,4] as well as that
of others, how understanding known NLC and NAC materials can inform
material design, and how the versatile chemistry of molecular frameworks
the connecting of cationic metal nodes with anionic molecular linkers in one
or more dimensionsallows for the targeting, enhancing and coupling of
functionalities.Structural motifs identified point towards strategies for designing
the next-generation of these materials, including the simple wine-rack,
honeycomb and spring mechanisms, where hinging about nodes requires
volume reduction by simultaneous expansion and contraction in perpendicular
directions.
[1] R. Baughman, S. Stafstrom, C. Cui et al., Science, 1998, 279, 15221524
[2] A. B. Cairns et al., Phys. Chem. Chem. Phys., 2015, 17, 2044920465
[3] A. B. Cairns, J. Catafesta, C. Levelut, et al., Nature. Mater., 2013,12, 212216
[4] S. A. Hodgson, J. Adamson, S. J. Hunt, et al., Chem. Commun., 2014, 50, 5264
5268.
307
Laser annealing after a kinetically hindered phase transition

in the pyrochlore La2Sn2O7: A method for true structure
determination and a pathway to recovery
Christian Childs1, S. Petitigirard2, A.L. Hector3, C.J. Pickard4,
J. Smith5, A. Salamat1
Dept of Physics and Astronomy and HiPSEC, Univ. of Nevada Las Vegas,
Las Vegas, NV, USA
2
Bayerisches GeoInstitut (BGI), Univ. of Bayreuth, Bayreuth, Germany
3
Chemistry, Univ. of Southampton, Southampton, UK
4
Dept of Materials Science & Metallurgy, Univ. of Cambridge, Cambridge, UK
5
High Pressure Collaborating Access Team at Advanced Photon Source, Geophysical Laboratory,
Carnegie Institution of Washington, Argonne, IL, USA
1
POSTER 8
There is significant interest in identifying novel materials for use in radioactive

waste applications and studying their structural properties. Previous research
has shown that pyrochlore compounds might be promising candidates
for such purposes. In an attempt to obtain a broader understanding of the
structural stability of these compounds, we have investigated the pyrochlore
La2Sn2O7under extreme conditions: high temperature isobaric and high-pressure
isothermal study. Both quasi-hydrostatic and non-hydrostatic isothermal high
pressure compression runs were undertaken to reveal alternative structural
transformations and studied using synchrotron angle-dispersive X-ray diffraction
and Raman scattering techniques. Compression using He as a quasi-hydrostatic
pressure transmitting medium permitted the observation of a new high pressure
phase via a kinetically hindered first-order phase transition that begins at 49
GPa and finally goes to completion at 61 GPa. Alternatively, the non-hydrostatic
compression, using no pressure-transmitting medium, revealed the emergence
of a phase transition at 46 GPa. However, it appears that this process occurs
via a stress-induced pathway and in fact transforms into an amorphized phase
by 67 GPa. Annealing the amorphized phase, through laser heating, at 70GPa
allows us to crystallize the high pressure phase which is recoverable to ambient
conditions. We have performed ab-initio random structure searching (AIRSS) to
compare to our x-ray diffraction results.
308
High pressure stability of perovskite metal organic

framework [(CH3)2NH2][Mn(HCOO)3]
Abhishek Chitnis1, N. Garg1, M. Maczka2, H. Bhatt1, M.N. Deo1,

S. Sharma1
High Pressure & Synchrotron Radiation Physics Division, Bhabha Atomic

Research Centre, Mumbai, India
2
Inst. of low temperature and structure research, Polish academy of Sciences,
Wroclaw, Poland
1
POSTER 9
Dimethyl ammonium metal formate is an important member of the metal

organic framework (MOF) family. These compounds are known to exhibit
multiferroicity, order disorder transition, dielectric transition at low temperature.
It is well established that the low temperature ferroelectric ordering in pervoskite
structured DMA metal formates is due to the hydrogen bond ordering
which results in a structural transition from centrosymmetric R-3c to non
centrosymmetric Cc phase. At the ferroelectric transition manganese formate
shows a magnetoelectric coupling in the paramagnetic state which has been
shown to be a consequence of the magnetoelastic effect. Though these MOFs
have been extensively studied at low temperature the high pressure studies are
very few. To probe the effect of pressure on the disordered hydrogen bond and
the HCOO- chains we studied the high pressure behavior of manganese formate
with the help of IR and Raman spectroscopic studies upto 22 GPa. A pressure
induced phase transition was initiated at ~ 4.5 GPa and was complete by 7 GPa
indicating its first order nature. The pressure evolution of the various modes
of vibrations indicates that at ~5 GPa distortion of formate cages accompanied
by a rearrangement of the DMA cation due to hydrogen bond ordering. A few
vibrational modes which were Raman active at room pressure became IR active
in the high pressure phase, which indicates that the high pressure phase could be
non centrosymmetric. Detailed results will be discussed.
309
Diffuse scattering and anomalous lattice dynamics in

cadmium cyanide
Chloe S. Coates1, V.E. Fairbank1, A.L. Thompson2, R.I. Cooper2,
E. Spencer3, N.L. Ross3, B. Slater4,A.L. Goodwin1
Dept of Chemistry, Univ. of Oxford, Inorganic Chemistry Laboratory,

Oxford, UK
2
Dept of Chemistry, Univ. of Oxford, Chemistry Research Laboratory,
POSTER 10
Oxford, UK
3
Dept of Geosciences, Virginia Tech, Derring Hall, Blacksburg, VA, USA
4
Dept of Chemistry, Univ. College London, London, UK
1
Whilst traditionally crystallography has been applied uniquely to ordered

materials, there is burgeoning interest in the analysis of disordered materials
and how they might be exploited for their functionality. Cd(CN)2 has attracted
considerable interest for its very strong negative thermal expansion. It is an
ideal candidate for investigation because of the clear link between disorder and
its intriguing thermal behaviour. Cd(CN)2 adopts the diamondoid topology of
cubic ice-VII, well known (and well-studied) for its hydrogen disorder, replacing
O atoms for Cd2+ cations and H atoms with CN- ions. There exist two types of
disorder within the framework. The cyanide anions are orientationally disordered:
although the C and N atoms are crystallographically indistinguishable, 113Cd
NMR studies have shown that the favoured configuration of cyanides mimics
the two-in-two-out ice-rules configuration for H atoms in ice; whereby each
Cd centre bonds preferentially to two C and two N atoms. In addition to this
there is correlated dynamic disorder of the Cd centres. The highly structured
diffuse scattering evident in the diffraction pattern for Cd(CN)2 is caused by
displacements (~1) of the Cd along the <100> away from the central tetrahedral
position, which are correlated throughout the structure.
The main indication that suggests that this disorder is responsible for this
materials intriguing physical properties is the failure of DFT calculations to
account for the observed behavior. Here, we show that preliminary studies into
the elastic constantsof Cd(CN)2, obtained via high-pressure single-crystal X-ray
diffraction and nanoindentation, differ by an order of magnitude compared to
DFT calculations. An understanding of the origin of negative thermal expansion
in this family of materials will provide valuable insight into the relationship
between disorder and material properties, and give an indication as to how we
might tune the functionality of framework materials.
310

Davide Comboni1, P. Lotti2, G.D. Gatta1, L. Pastero3
Dip. di Scienze della Terra, Univ. degli Studi di Milano, Milan, Italy
Elettra, Sincrotrone Trieste S.c.P.A., Trieste, Italy
3
Dip. di Scienze della Terra, Univ. degli studi di Torino, Turin, Italy
1
2
POSTER 11
Aluminophosphate are objects of a growing research interest

due to their potential technological and industrial applications
[e.g 1,2]. Their large channels serve as ideal host for organic compounds and small
polymers. Among those, AlPO4-5 is a synthetic zeolite characterized by an openframework of (P,Al)O4 tetrahedra. The tetrahedra are connected to form six- and
twelve-membered rings, in such a way that a large channel (~7.3), parallel to
the [001] direction, occurs. Klap et al. [3] underlines that every crystal of AlPO45 is built up by three different microdomains, in which the positions of the
framework oxygen atoms are slightly different; the main effect of the structural
disorder is the very large anisotropic displacement parameters of the framework
oxygens. We performed two in situ single-crystal synchrotron X-ray diffraction
experiments using both penetrating (methanol:ethanol:H2O mix, m:e:w) and
non-penetrating (silicon oil) pressure media [4]. The structure refinements
showed that: 1) for compression in m:e:w mix, H2O molecules are absorbed at
low-P regime, forming a H2O-network by H-bonding interaction; 2) the elastic
parameters of the super-hydrated AlPO4-5 are different if compared to the one
compressed in silicon oil; 3) the structural deformation mechanisms of superhydrated and regular AlPO4-5 are different; 4) evidence of a incommensurately
modulated structure occur (according to [3]), and there is an evolution of the nonBragg reflections with pressure.
The author acknowledges the Italian Ministry of Education, MIUR-Project:
Futuro in Ricerca 2012 - ImPACT- RBFR12CLQD.
[1] Tang Z.K. et al. Applied Physics Letters 1998; 73, 2287-2289; [2] Yang W.S.
et al. Microporous and mesoporous materials 2016; 219,87-92. [3] Klap G.J. et
al. Microporous and mesoporous materials 2000; 38, 403-412. [4] Gatta, G.D.
Microporous and Mesoporous Material 2010; 128, 7884.
Keywords: zeolites, AlPO4-5, high pressure.
311
Crystal engineering of multicomponent constructs and the

impact of high pressure
Lauren Evelyn Connor1,2, G. Halbert1,2, I.D.H. Oswald1,2
Strathclyde Inst. of Pharmacy and Biomedical Sciences, Univ. of Strathclyde,

Glasgow, UK
2
EPSRC Centre for Continuous Manufacture and Crystallisation, Univ. of
Strathclyde, Glasgow, UK
1
POSTER 12
Solid state modification such as cocrystallisation can improve

the physicochemical properties of the end multicomponent construct without
altering the chemical composition of the individual components. High pressure
is known to alter the thermodynamic stabilities of materials with the potential
for isolating materials that have not been observed before. This present study
investigates the challenging cocrystalline structure of the non-steroidal, antiinflammatory indomethacin with the sweetener component saccharin. Cocrystals, obtained by slurry and solvent evaporative techniques, were chosen
and compressed to 6.33GPa using a Diamond Anvil Cell. Single crystal X-Ray
diffraction measurements show that the co-crystal remains in the same phase
throughout the compression with a triclinic, P-1 unit cell containing a busy
116 atoms with plenty of void space to allow for compression in the originally
1143.93 volume unit cell. The increase in pressure up to 6.33GPa leads to an
overall compression of the unit cell axes with a large decrease in the b-axis as
compared to the c-axis. The c-axis lies in the same direction as the main body of
the indomethacin and saccharin molecules making this axis fairly stable against
compression. Diagonal arrangements of the molecules within the unit cell allow
for sheets of void space to dissipate, contributing to the large decrease in the
b-axis.
312
Boundaries of martensitic transition of lithium

Shanti Deemyad, M. Dunuwille
Dept of Physics and Astronomy, Univ. of Utah, Salt Lake City, UT, USA
I present our studies of the low temperature structural phase

diagram of lithium isotopes under pressure up to 30GPa. In
this study we used x-ray diffraction to examine the structures
of lithium isotopes and the hysteresis in the structural phase
boundaries of lithium under hydrostatic conditions.
POSTER 13
313
Hirshfeld surface analysis and magnetic behaviour of a

pyrazole-based copper complex
Amani Direm, N. Benali-Cherif
POSTER 14
Laboratoire des Structures, Proprits et Interactions Inter-Atomiques

LASPI2A, Facult des Sciences et Technologie, Univ. Abbes Laghrour,
Khenchela, Algrie
Metal organic frameworks (MOFs) consist of metal ions

or clusters often coordinated to rigid organic molecules to
form one-, two-, or three-dimensional structures. MOFs are also known as
coordination polymers which are the inorganic or organometallic polymer
structures containing metal cation centers linked by organic ligands. The
chemical and pharmacological properties of the pyrazoles have been investigated
extensively, due to their chelating ability with metal ions [1] as terminal [2,3] or
bridging ligands [4] and, precursors for synthesis of various multi-nitrogen donor
ligands in the coordination, bio-inorganic and organometallic chemistry [5].
Its worth to note that the crystal structure of the discrete complex transDichlorotetrakis(1H-pyrazole-N2)copper(II) [6] has been described three times in
the earlier literature [9-12]. However, its magnetic behavior has not been reported.
Moreover, the non-classical intermolecular interactions within this complex, by
means of the Hirshfeld surface analysis, will be investigated herein for the first
time. The Hirshfeld surfaces used to define the intermolecular environment of the
molecules within the crystal together with the 2D-figerprint graphics allowing
exploring the properties and the occurrence of each intermolecular contact in the
studied complex will be discussed in detail [13].
References :
[1]V. Montoya, J. Pons, J. Garcia-Antn, X. Solans, M. Font-Bardia, & J. Ros, Inorg. Chim.
Acta. 360(2007) 625637. [2]T. Itoh, Y. Fuji, T. Toda, Bull. Chem. Soc. Jpn 69(1996)
1265. [3]Y.J. Sun, P. Cheng, S.P. Yan, D.Z. Liao, Z.H. Jiang & P.W. Shen, J. Coord. Chem.
55(2002) 363. [4]S. Trofimenko, Chem. Rev. 72(1972) 497. [5]M.K. Ehlert, S.J. Rettig, A.
Storr, R.C. Thompson & J. Trotter, Can. J. Chem. 67(1989) 1970. [6]Direm, A., Tursun,
M., Parlak, C. & Benali-Cherif, N. (2015). J. Mol. Struc. 1093, 208218. [9]J. Reedijk,
Recl. Trav. Chim. 89(1970) 993. [10]A. Mighell, A. Santoro, E. Prince & C. Reimann,
Acta Cryst. B31(1975) 2479. [11]Y.J. Sun, P. Cheng, S.P. Yan, D.Z. Liao, Z.H. Jiang & P.W.
Shen, J. Mol. Struct. 597(2001) 191. [12]Y.-H. Xing, J. Han, B.-L. Zhang, X.-J. Zhang, Y.-H.
Zhang & G.-H. Zhou. Acta Cryst. E62(2006) m3354m3356. [13]M. A. Spackman & D.
Jayatilaka, CrystEngComm. 11(2009) 1932.
314
Theoretical and Experimental Study of the High-Pressure

Isosymmetric Phase Transition in lead fluoride, PbF2
Rajkrishna Dutta1, C.V. Stan2, C.E. White3,4, T.S. Duffy1
Dept of Geosciences, Princeton Univ., Princeton, NJ, USA

Dept of Chemistry, Princeton Univ.,Princeton, NJ, USA
3
Dept of Civil and Environmental Engineering, Princeton University,
Princeton, NJ, USA
4
Andlinger Center for Energy and the Environment, Princeton University,
Princeton, NJ, USA
1
2
POSTER 15
The high-pressure behavior of PbF2 has been controversial. Under compression

many AX2 compounds follow a canonical transition sequence from the fluoritetype (8-fold coordination) to the cotunnite-type (9 CN) to the Ni2In-type phase
(11 CN). Lead fluoride, however, is instead reported to undergo an unusual
isosymmetric phase transition from the cotunnite phase to a Co2Si-like phase (9
CN) at ~10 GPa1.
We have examined the high-pressure behavior of PbF2 using in-situ synchrotron
x-ray diffraction and first-principles calculations to 70 GPa. Both experiment and
theory shows that lattice parameters display highly anomalous trends from 9-21
GPa, but there is no discontinuous change in the x-ray diffraction pattern or unit
cell volume. We confirm that cotunnite-structured -PbF2 (Pnma) undergoes a
transition to a Co2Si-type structure (Pnma) at high pressures. Our calculations
also reveal the detailed atomic rearrangements associated with the development
of an extra Pb-F bond in the high-pressure phase. At P > 9 GPa, both the lead and
fluorine ions begin to reorient themselves as an additional fluorine atom, initially
outside the 9-fold coordination polyhedron of cotunnite, approaches it. At P
~21 GPa, the transformation is completed with an increase in the coordination
number from 9 to 10.
Our results are consistent with an isosymmetric phase transition occurring over
a broad pressure interval. Haines et al.1 used empirical systematics3 of lattice
parameter ratios to conclude that the high-pressure phase is Co2Si like. Using
our calculated atomic positions and electron densities, we show that the highpressure phase has the Co2Si type structure and that empirical lattice parameter
relationships for these phases need to be modified based on our results.
References
1
Haines et al Phys. Rev. B 57, 7551 (1998).
2
A. Costales et al., Phys. Rev. B 61, 11359 (2000).
3
W. Jeitschko, Acta Crystallogr. Sect. B 24, 930 (1968).
315
High-pressure -CaMgSi2O6: Is penta-coordinated silicon

common in the Earths mantle?
Yi Hu1,2, B. Kiefer3, P. Dera1,2
Dept of Geology and Geophysics, School of Ocean and Earth Science and
Technology, Univ. of Hawaii at Manoa, Honolulu, HI, USA
2
Hawaii Inst. of Geophysics and Planetology, School of Ocean and Earth
Science and Technology, Univ. of Hawaii at Manoa, Honolulu, HI, USA
3
Dept of Physics, New Mexico State Univ., Las Cruces, NM, USA
1
POSTER 16
Earth is a rocky planet and is dominated by silicates. Si4+, due to its electronic
configuration, prefers 4- or 6- fold coordination. Crust and upper mantle of our
planet feature minerals with silicon almost exclusively in 4-coordinated sites (e.g.
quartz, pyroxenes and olivine), whereas minerals with silicon in 6-coordinated
sites dominate the transition zone and the lower mantle (e.g. stishovite, perovskite
and akimotoite). 5-coordinated Si4+ is observed in silicate glasses and melts upon
compression as intermediate states. Crystalline silicates with Si4+ in 5-coordinated
sites, though rare, have been previously reported in CaSi2O5 and MgSiO3 and can
provide important information about phase transition pathway. Diopside, with
formula of CaMgSi2O6 is a Ca, Mg endmember of pyroxene which has a space
group of C2/c in the upper mantle. Here, we show results of a compression study
of natural diopside with ~10% Fe2+, which at pressures above ~ 50 GPa, transforms
to a new P21/c phase features Si4+ in 5- and 6- coordinated sites (-diopside),
whereas below 50 GPa, on decompression, the coordination scheme changes to 4and 6- (-diopside) as is reported by previous studies. Density functional theory
also predicted the existence of -diopside by relaxing -diopside. The new exotic
structure constitutes another example of pentavalent silicon in metastably overcompressed crystalline silicates, suggesting that penta-coordinated Si4+ may be
present in the transition zone and the lower mantle in appreciable quantities not
only in glasses and melts, but also in the coldest parts of subduction zones, and
may have significant consequences for controlling phase transition kinetics and
deformation mechanisms of silicate rocks within the slab.
316
The structure of siderite melt at high pressure

Jessica M. Hudspeth1, C. Sanloup1, B. Cochain1, V. Alfonina2,
Z. Konopkova3, W. Morgenroth4
Sorbonne Univ., Paris, France

Centre for Science at Extreme Conditions and School of Physics and
Astronomy, Univ. of Edinburgh, Scottish Univ. Physics Alliance, Edinburgh, UK
3
Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany
4
Goethe Univ., Frankfurt, Germany
1
2
POSTER 17
Carbonate melts are rare magmas with only a single active volcano (Oldoinyo
Lengai,Tanzania1). They are of fundamental interest for their role in the Earths
deep carbon cycle and of immense economic importance due to their affinity
for REE strategic metals (niobium, uranium, tantalum, etc). Carbonate melts are
ionic liquids consisting of CO32 anions and metal cations which, unlike silicate
melts, can not form network structures through polymerisation2. Despite their
atomic structure being fundamental for controlling their physical and chemical
behaviour, very few structural studies have been reported and these have been
largely computational2,3.
The structure of siderite melt, FeCO3, is of interest for a number of reasons:
1. FeCO3 forms a complete solid solution with MgCO3, which has been suggested
as one of the major carbon-containing phases in the lower mantle4.
2. A high-spin to low-spin transition for Fe2+ occurs in crystalline FeCO3 at
~50GPa5. Such a transition in FeCO3 melts could have significant implications for
the solubility of Fe in MgCO3 melts and for Fe-partitioning in the lower mantle.
3. There is recent experimental and theoretical evidence for a new crystalline
phase in (Mg,Fe)CO3 above ~80GPa consisting of corner sharing CO4 tetrahedra6.
If a transition to tetrahedrally coordinated CO4 occurs in the melts it would
drastically change the melt properties since unlike CO3, CO4 can form
polymerisable networks2,6.
X-ray diffraction in diamond anvil cells (DACs) using either laser or resistive
heating provides a method for investigating melt structures in situ. Here we
present preliminary results for siderite, FeCO3, melts at pressures of up to 90GPa.
References: 1Krafft and Keller, Science 245:168-170, 1989, 2Jones et al., Rev.
Mineral. Geochem. 75:289-322, 2103, 3Genge et al., Earth Planet. Sc. Lett. 131:225238, 1995, 4Isshiki et al., Nature 427:60-63, 2003, 5Lavina et al.,Phys. Rev. B,
82:064110, 2010, 6Boulard et al., Nat. Commun. 6:6311, 2015
317
Crystal structure studies of SAM dependent

Methyltransferase from Pyrococcus horikoshii
S. Madan Kumar1, K.J. Pampa2, N.K. Lokanath3
PURSE Lab, Mangalagangotri, Manglore Univ., Manglore, India

Dept of Studies in Physics,Univ. of Mysore, Manasagangotri, Mysore, India
3
Dept of Studies in Microbiology, Univ. of Mysore, Manasagangotri, Mysore,
India
1
2
POSTER 18
The methyltransferases (MTs) are the enzymes involved in

the methylation to perform various cellular processes such as biosynthesis,
metabolism, gene expression, protein trafficking and signal transduction.
The cofactor S-adenosyl-L-methionine (SAM) is used for catalysis by SAMdependent methyltransferases. The crystal structure of Prococcus horikoshii
SAM-MT is determined to a resolution of 2.1 using X-ray diffraction method.
The monomeric structure consists Rossmann-like fold (domain I) and substrate
binding domain (domain 2). The cofactor SAM molecule was bound at the cleft
between the two domains of the MT and interacts with the residues from other
monomer. The SAM is involved in oligomerization. The thermostability analysis is
performed by calculating thermostable parameters.
318
One-Dimensional Chains of Mn12 Single-Molecule

Magnetsand the Effects of Pressure
Christos Lampropoulos1, S.A. Corrales1, J.M. Cain1,
K.A. Uhlig1, T. Jenkins1, D. Pistey1, M. Garnero1, A.M. Mowson2,
C. Papatriantafyllopoulou3,4, M.K. Peprah5, A. Ozarowski6,
A.J. Tasiopoulos3, G. Christou2, M.W. Meisel5, T.M. Pekarek7
Dept of Chemistry, Univ. of North Florida, Jacksonville, FL,USA
Dept of Chemistry, Univ. of Florida, Gainesville, FL,USA
3
Dept of Chemistry, Univ. of Cyprus, Cyprus
4
Current: NUI Galway, Ireland
5
Dept of Physics, University of Florida, Gainesville, FL, USA
6
National High Magnetic Field Lab, Tallahassee, FL, USA
7
Dept of Physics, University of North Florida, Jacksonville, FL, USA
1
POSTER 19
The [Mn12O12(O2CR)16(L4)] family (R = various; L = terminal ligand) of clusters

holds a special place in molecular magnetism; they are the most well-studied
single-molecule magnets (SMMs). Targeted linkage of these SMMs has now been
achieved for the first time. The resulting chain structures have been confirmed
crystallographically, and the magnetic properties, up to 1.14 GPa, and high-field
electron paramagnetic resonance spectra have been collected and analyzed.[1]
Examination of the crystal structure under pressure could shine light into the
origin of the altered magnetic properties under pressure. A complete pressure
study is on the way with x-ray, HFEPR, and magnetometry under pressure.
319
Effect of pressure on isoreticular metal organic frameworks

Arianna Lanza1,2, L.S. Germann3, M. Fisch1,2, N. Casati2,
P. Macchi1
Dept of Chemistry and Biochemistry, Bern Univ., Bern, Switzerland

Lab. of Synchrotron Radiation, Paul Scherrer Inst., Villigen, Switzerland
3
Max-Planck Inst. for Solid State Research, Stuttgart, Germany
1
2
POSTER 20
MOFs with stereochemically accessible unsaturated metal

centres could in principle allow chemisorption of small
molecules on the metal sites. This characteristic, together with framework
flexibility, are desirable features for the design of promising catalysts, selective
sieves or absorbents. Moreover, by varying metal centres, their oxidation state,
organic linkers, guest molecules, stereochemical features etc., the potential and
complexity of MOFs can be tuned towards to the desired properties. Efforts to
rationalize the synthesis of frameworks with specific features would therefore
benefit from comparative studies involving systematic variations of their
structure, which can be induced by external stimuli (temperature, pressure)
as well as by chemical modifications. In this work, we investigated the role of
controlled structural modifications on the physico-chemical properties of a family
of isostructural MOFs.
A flexible and porous MOF, based on CoII connectors and benzotriazolide-5carboxylato linkers, was found to selectively react with guest molecules trapped
in the channels during the sample preparation or after an exchange process.
Upon compression or cooling, the system underwent a reversible, non-oxidative
nucleophilic addition of the guest molecules to the metal ions. Depending on the
guests, stepwise increase in the metal coordination up to its saturation could be
achieved.
Isoreticular MOFs were obtained by replacing the CoII nodes with ZnII or
MnII and adjusting the synthetic conditions. The obtained MOF series shows
in principle the same kind of reactivity but with different sensitivity to guest
exchange, temperature variations and pressure-induced breathing.
320
Preliminary results of FTIR and Raman study of hydrous

enstatite
Ching-Chien Li1, Y.Y. Chang2, W.P. Hsieh2, J. Kung1
1
2
Dept of Earth Science, National Cheng Kung Univ., Tainan, Taiwan

Inst. of Earth Science, Academia Sinica, Taipei, Taiwan
Pyroxenes are the second abundant minerals that composed

POSTER 21
the Earths upper mantle. These minerals are also important
nominally anhydrous minerals (NAMs) that particularly interest
researchers in their ability of incorporating relatively large amount of water
under mantle pressure and temperature condition(Mierdel et al., 2007; Sundvall
and Stalder, 2011).In order to study the effect of water on crystal structure
and physical properties of pyroxenes, synthesized enstatite single crystals
wereexaminedby FTIR and Raman spectrometer under ambient condition.FTIR
spectra confirmed the generalexistenceof OH in all the samples synthesized
under hydrous enviroment in this study. Some extra IR absorption bands (~2850,
~2929, ~3470,~3520, and ~3550 cm^-1)were found in these spectra but did not
appeared in most previous studies.Raman peaks seems to appear at similar
positions as IR bands. Raman peaks includea very broad band at ~2800, and other
sharper bands at ~3060, ~3360, ~3550, ~3600, and ~3690 cm^-1. Bands observed
at ~3550, ~3600, and ~3690cm^-1 are very close to those described in BolfaCasanova et al. (2014).However, peaks at ~2800, ~3060, and ~3360 cm^-1 have
not been reported in our knowledge.The differences in spectra may suggest some
clues of how the hydroxyl existed in the crystal structure.The study is currently
undergoing so we expect to show more detailed results in the session. With the
study of dry and hydrated enstatite using IR and Raman spectrum, we hope to
shed some light into the research of the hydration mechanism and the effect of
water on physical properties of pyroxenes.
321
Raman spectroscopy of monohydrated L-asparagine up to 30

GPa
J. Alves LimaJr.1, J.A.F. Silva1, P.T.C. Freire1, J. Mendes Filho1,
F.E.A. Melo1, A.J.D. Moreno2, A. Polian3
Dep. de Fsica, Univ. Federal do Cear, Fortaleza, Brazil
Univ. Federal do Maranho, Bacabal, Brazil
3
Inst. de Minralogie, de Physique des Matriaux et de Cosmochimie,
Sorbonne Univ., Paris, France
1
2
POSTER 22
Amino acid crystals are important systems to investigate chemical bonds of

biochemical interest, and in the past twenty years, many studies have focused
on their vibrational and structural properties. In this work we investigate the
Raman spectrum of the amino acid L-asparagine monohydrated under high
pressure, from 1 bar to 30 GPa in order to search the vibrational behavior of the
crystal and to infer the occurrence of pressure-induced phase transitions. The
pressure value reached here is twice the pressure where L-alanine was observed
to present a solid - amorphous phase transition but up to the maximum pressure
reached in our experiments, no evidence of amorphization was found. However,
several modifications in all spectral range of the Raman spectrum (30 3600
cm-1) suggest that monohydrated L-asparagine undergoes solid - solid phase
transitions. It was possible to note several modifications of the Raman spectrum
during compression, suggesting the occurrence of a phase transition at ~ 10 GPa,
although some modifications in the ranges 2.1 and 3.1 GPa and 15.0 17.0 GPa
should suggest some conformational change of the molecules. Additionally, we
have observed that when pressure is released to atmospheric pressure the original
spectrum is recovered, indicating that the phase transitions are reversible.
322
High-pressure studies of biodiesel

Xiaojiao Liu1, C.R. Pulham1, K. Lewtas1, P. Dowding2
School of Chemistry & Centre for Science at Extreme Condition, Univ. of

Edinburgh EastCHEM, Edinburgh, UK
2
Infineum UK Ltd, Abingdon, England, UK
1
Research into air pollution has shown that the combustion

POSTER 23
of fossil fuels contributes to 98% of global carbon dioxide
emissions. There is an urgent requirement to reduce CO2
emissions by reducing consumption of fossil fuels. Hence there is growing interest
in the use of biodiesel obtained from sustainable, biomass-based sources. In 2003,
the EU set a target for the use of biodiesel of 5.75% of total fuel consumption by
2010. The current target for 2020 is 10 %.1
Whilst biodiesel has many advantages, it suffers from poor performance at
both low temperature and high pressure. It is notable that biodiesel has poor
high-pressure performances. Biodiesel crystallises under the high pressures
experienced in common-rail and injector systems within diesel engines. The
study of pressure-induced crystallisation of biodiesel is therefore essential for
understanding and hence improving engine performance with this fuel.
Diamond-anvil cells and high-pressure piston cylinders are employed in this
project to create high-pressure environments. The study shows that biodiesel
crystallises at 0.16 GPa under ambient conditions. A combination of optical
microscopy Raman spectroscopy and synchrotron X-ray powder diffraction shows
a series of crystalline phase transitions in the pressure range from 0.36 GPa to
4 GPa. A study of the high-pressure performance of methyl stearate, one of the
model compounds of biodiesel, is a practical way to understand biodiesel. High
resolution synchrotron XRPD data of methyl stearate demonstrates two phase
transitions in the pressure range from 0.1 GPa to 6 GPa. The results of these
studies show different crystalline behaviours under different pressure ranges. This
information is valuable for optimizing biodiesel performance under high-pressure
conditions, e.g. identification of additives that modify crystal size and morphology
at elevated pressures.
323
High-pressure behavior of natural borate colemanite. An in

situ synchrotron single-crystal X-ray diffraction study
Paolo Lotti1,2, G.D. Gatta1, D. Comboni1, M. Merlini1,
H-P Liermann3
Earth Sciences Dept., Univ. degli Studi di Milano, Milan, Italy
Elettra Sincrotrone Trieste S.c.P.A., Trieste, Italy
3
Photon Sciences, Desy, Petra-III, Hamburg, Germany
1
2
POSTER 24
Colemanite is an inoborate compound and a common

constituent in natural borate deposits. In addition, it is an economically
relevant mineral commodity, not only as a primary source for B, but also for its
applications in the production of lightweight concretes and ceramics. Despite
its relevance in industrial applications, its elastic behavior, phase stability and
structure evolution with pressure have never been investigated. Here we report
the high-P behavior of a natural colemanite based on an in-situ synchrotron
single-crystal X-ray diffraction study performed at the P02.2 beamline at PETRAIII, Hamburg, Germany.
Colemanite, which crystallizes in the monoclinic P21/a space group (a = 8.712 ,
b = 11.247 , c = 6.091 , = 110.12, V = 560.4 3), undergoes a reconstructive
phase transition between 13.95 and 14.91 GPa, toward a monoclinic polymorph
(S.G.: P21/n, a = 11.726(11) , b = 10.206(1) , c = 23.45(3) , = 95.07(9), V =
2796(4) 3, at 14.91 GPa). A III-order Birch-Murnaghan EoS fit leads to a refined
bulk modulus at ambient conditions of 76(8) GPa [K V= 4.4(10)], for colemanite
in the phase stability field: 0.0001-13.95 GPa. The structure of colemanite is made
by infinite chains of corner-sharing B-polyhedra alternated by chains of cornersharingCa-polyhedra (coordination number 8). Of the three crystallographically
independent B sites, one shows a triangular coordination and the others a
tetrahedral coordination. In the high-P polymorph, only three over eighteen
independent B-sites (1/6) show a triangular coordination, the other fifteen
being B(O,OH)4 tetrahedra. Two independent corner-sharing borate chains are
interconnected through corner and edge-sharing chains of Ca-polyhedra (C.N.
8 or 9). X-ray diffraction patterns collected during P-release show that the phase
transition is completely reversible and colemanite fully recovers its starting
structural features.
324
Status of the dedicated high pressure diffraction beamline

Xpress at Elettra Sychrotron Trieste
B. Joseph1, M. Polentarutti2, Paolo Lotti2, N.K. Varshney1,
G. Bais2, S.M. Sharma3, D.D. Sarma4, A. Lausi2
IISc-ICTP Fellow, Elettra Sincrotrone Trieste S.c.P.A., Trieste, Italy
Elettra Sincrotrone Trieste S.c.P.A., Trieste, Italy
3
Bhabha Atomic Research Center, Trombay, Mumbai, India
4
Indian Institute of Science, Bangalore, India
1
2
POSTER 25
Recently with the opening of the Xpress beamline [1], the high pressure
diffraction user community of the Elettra synchrotron facility have a dedicated
experimental set up at their disposal. This new beamline is part of a scientific
partnership between India and Italy under a project administered through the
IISc Bangalore, for the development of a macromolecular and a high pressure
x-ray diffraction facilities, respectively XRD2 [2] and Xpress. A multipole
superconducting wiggler (SCW) is the source of these two beamlines. A liquid
nitrogen cooled silicon single crystal (cut along the (111) direction) hosted in the
splitter chamber in the Front-End section intercepts the beam from the source
(SCW) and directs it to the focusing mirror of the Xpress at a fixed energy of 25
keV. At this energy, the SCW provides a factor of 14 higher photon flux compared
to the permanent magnet wiggler of XRD1, the existing diffraction beamline. The
beam is focused using a toroidal mirror of 1.4 m long and 2.9 mrad grazing angle
with a Pt coating to achieve 80% reflectivity at 25 keV. Focused beam from the
mirror is further optimized by collimators (presently 80 micron diameter) to have
intense and well defined monochromatic beam required for the high pressure
x-ray diffraction experiments. On-line pressure monitoring is achieved through a
ruby fluorescence microscope connected side-by-side to the final beam collimator
stage. The present experimental stage is equipped to host room temperature high pressure powder diffraction measurements using various kinds of Diamond
Anvil Cells (DAC) in the pressure range 0-50 GPa. An image plate MAR345, with
a controllable linear movement along the beam direction at two fixed vertical
positions is available for recording the diffraction pattern. An upgrade to perform
single crystal diffraction will be taken up very soon.
[1] http://www.elettra.eu/elettra-beamlines/xpress.html
2] http://www.elettra.eu/elettra-beamlines/xrd2.html
325
Compression of most frequent intermolacular forces in

toluene polymorphs
Jdrzej Marciniak
Adam Mickiewicz Univ., Pozna, Poland
C-H hydrogen bonded motifs have been determined in four

polymorphs of toluene. New toluene phases: monoclinic phase
POSTER 26
III (space group P21) and orthorhombic phase IV (space group
Pbca) have been obtained between 1.11.5 GPa, and 1.272.1 GPa, respectively.
While the 2-dimensional aggreagation is characteristic of low-temperature
toluene polymorphs I and II, phases III and IV reveal a 3-dimensional C-H
interactions net. The most frequent C-H bonding motif involves the methyl
H-donor and the acceptor atoms C3 and C5. The stability regions of toluene
polymorphs outlined in the pressure-temperature phase diagram.
326
Elastic geobarometry: principles and practice

Mattia Luca Mazzucchelli1, R.J. Angel2, P. Burnley3,
M.C. Domeneghetti1, F. Nestola2, M. Alvaro1
Dept of Earth and Environmental Sciences, Univ. of Pavia, Pavia, Italy

Dept of Geosciences, Univ. of Padua, Padua, Italy
3
Dept of Geosciences and High Pressure Science and Engineering Center,
Univ. of Nevada, Las Vegas, NV, USA
This work is supported by MIUR-SIR grant MILE DEEp (RBSI140351) to
M. Alvaro, and ERC starting grant 307322 to Fabrizio Nestola.
1
2
POSTER 27
The vast majority of high-pressure experiments are performed under

hydrostatic stress conditions with the sample immersed in a fluid pressure
medium and therefore subject to equal normal stresses and no shear stress.
The volume change of the sample is defined by the Reuss bulk modulus K(Reuss)=
(s11+s22+s33+2(s12+s13+s23))-1 = -V*(P/V). The variation of the bulk modulus
with P is defined by the samples Equation of State (EoS).
Minerals in rocks often completely enclose other minerals as inclusions, trapped
when the minerals grew at high P and T in the Earth. This is a completely
different situation from a conventional high-P experiment because the inclusions
are surrounded not by a fluid but by a strong solid. At the time of growth, both
the inclusion and host had the same P, T and the inclusion fitted exactly within
the host. When the external P on the host mineral is changed, the host responds
as V/V= -P/K(host). But the inclusion is constrained to the same V/V as the
host, so its pressure changes as P(inc)= P*K(inc)/K(host). Similar expressions can
be developed for T changes. As a consequence, a solid inclusion trapped within
another material (e.g. in diamonds and other high-pressure minerals) develops
a different pressure than the external pressure, which depends on the contrast
of the elastic properties. These concepts have been known for a long time, but
quantitative modelling of inclusion-host systems based on non-linear elasticity
theory and precise thermal-pressure EoS has only recently become available [1,2].
The measured residual P of inclusions can then be used to determine a line in P-T
space which represents possible conditions of entrapment, provided the host and
inclusion are isotropic and spherical. For anisotropic systems we are using Finite
Element Modeling to determine the deviations in behavior from the isotropic
theory.
References
[1] Angel et al (2014)AmMineral 99: 2146.
[2] Angel et al (2015) J Metamorph Geol 33: 80.
327
A moderate pressure cell for the small molecule beamline

I19 at the Diamond Light Source
Charlie McMonagle1, M. Warren2, D. Allan2, S. Moggach1
1
2
EaStChem School of Chemistry, The Univ. of Edinburgh, Edinburgh, UK

Diamond Light Source, Rutherford Appleton Laboratory, Didcot, UK
Since the invention of diamond anvil cells (DACs), they have

become the primary pressure cell design that has dominated
high pressure science when kbar pressures are required. They
have made data collection (both single-crystal and powder) routine, however they
are not without their limitations. Fine control of pressure is difficult to achieve
and measure accurately, particularly at lower pressures and often interesting
phase behaviour or compressibility can occur even below 1 kbar. Currently
there is a relative paucity of pressure cell designs made specifically for this lower
pressure regime.
Gas cells have been developed which allow 100s of bar of pressure to be applied
to a crystal using a compressed gas to study the uptake of gases into porous
materials 1 or chemical reactions at elevated temperature and pressure. 2-4 This
falls someway short of the kbars of pressure required to close the gap on DACs.
Here we present the development of a static liquid cell capable of reaching
kbar pressures that will help close the pressure gap between current gas cell
technology and DACs. To date we have collect data on a small organic (hexamine)
and a porous framework material up to 1,400 bar of hydrostatic pressure using
synchrotron radiation with the current generation of cells. This setup allows for
very fine pressure control and measurement (ca 1 bar) allowing a high degree of
crystallographic detail to be obtained without the usual limitations associated
with modern DAC technology. Further development and experimentation will
allow us to extend the pressure capabilitys and observe structural changes, phase
transitions and calculate with much greater precision the bulk moduli of soft
molecular materials.
1 Yufit, D. S. & Howard, J. A. K. J. Appl. Crystallogr. 38, 583-586, (2005).
2 Chupas, P. J. et al. J. Appl. Crystallogr. 41, 822-824, (2008).
3 Jensen, T. R. et al. J. Appl. Crystallogr. 43, 1456-1463, (2010).
4 Andrieux, J. et al. J. Appl. Crystallogr. 47, 245-255, (2014).
POSTER 28
328
Petrographic and thermodynamical studies on Salting-out

phenomenon induced by clathrate hydrates
Alba San Jos Mndez1, F. Izquierdo-Ruz2, O. Prieto-Ballesteros1
Dept Planetology and Habitability, Centro de Astrobiologa-INTA-CSIC,
Torrejn de Ardoz, Madrid, Spain
2
Dept Physical and AnalyticalChemistry,Oviedo Univ., Oviedo, Spain
1
POSTER 29
Salting-out is the chemical response of a system in which

electrolyte and non-electrolyte compounds compete with each
other for their dissolution in an aqueous environment. Commonly, when any
salt and gas are dissolved in water, gas solubility goes down if the ionic strength
increases, which is directly proportional to salt concentration. However, under
certain conditions, a similar phenomenon takes places in the opposite way.
One example of geological feature from salting-out phenomenon in terrestrial
environments is the called brinicle. They are tubular formations of ice, which
form in polar regions. This process implies salt exclusion, and therefore the
formation of brines in interstitial spaces of the ice pack. As water freezes in the
brine inclusions, it generates a volume expansion and the crystal lattice undergoes
an increment of internal pressure. This fact may provoke cracks in the ice pack
causing release of trapped brine. This dense, cold brine drains downwards from
sea ice freezing the water that is in direct contact with and forming a tube of ice.
MgSO4-CO2-H2O system is proposed as an approach of Europas ocean
composition. In this particular system, CO2 may form clathrate hydrates under
the properly conditions. Clathrate hydrates trap individual gas molecules in cages
what is the fact that makes these minerals to have a starring role in planetary
science due to their ability to act as efficient reservoirs of carbon-bearing species
like CH4 and CO2. In order to form clathrates, water molecules are removed from
the liquid phase. As a consequence, salt concentration increases and whether this
situation continues long enough, hydrated salts may precipitate.
Several simulation experiments are carried out at high pressure followed by
Raman spectroscopy analysis, which characterizes involved chemical species in
formation-dissociation of clathrate hydrates from salty water. Here we evaluate
how Europas geochemistry could be conditioned by this phenomenon.
329
Testing soft donor-acceptor intermolecular interactions with

high pressure
Fabio Montisci1, A. Lanza1,2, N. Casati2, P. Macchi1
1
2
Dept fr Chemie und Biochemie, Univ. Bern, Bern,Switzerland

Paul Scherrer Inst., Villigen, Switzerland
Weak intermolecular interactions have a fundamental role

in diverse fields such as protein folding, enzymatic reactions,
supramolecular chemistry, and crystal engineering. Hydrogen
bonding interactions, among the most common interactions and ubiquitous in
biological systems, have been therefore extensively studied. However, several nonhydrogen bonding interactions have receives less attention and still need to be
carefully investigated since they can also play a significant role in molecular selfassembly and single-crystal-to-single-crystal modifications (eg. polymorphism
and solid-phase chemical reactions). Among these, NO2NO2 interactions are
particularly interesting and somehow controversial; the nature of the interaction
has been debated, but various results suggest that it is indeed attractive and
comparable in energy to a weak hydrogen bond.
In this preliminary work, the crystal structure of 4-amino-4-nitrobiphenyl was
studied at different temperatures and different pressures, aiming to observe the
behaviour of NO2NO2 contacts under extreme conditions, when significant
changes of stereo-electronic properties can occur due to the smaller volumes in
which molecule are confined. A pressure-induced phase transition was observed
above 1.6 GPa, associated with a severe rearrangements of the molecular packing,
mainly driven by a NO2NO2 interaction. Several high-pressure DFT calculations
were also performed in order to select new possible study subjects in which the
nitro-nitro distances may reach smaller values.
POSTER 30
330
High-pressure solvates
Anna Olejniczak, A. Katrusiak
Faculty of Chemistry, Adam Mickiewicz Univ., Pozna, Poland
Pressure, temperature, solvent-type and the solution

concentration can efficiently affect the form of
1,4-diazabicyclo[2.2.2]octane salts (dabcoHX; X=I, Br, ClO4).
POSTER 31
Not only different unsolvated polymorphs could be obtained
but also various solvates. At ambient conditions those salts crystallize exclusively
in the unsolvated forms and are well known for their relaxor and ferroelectric
properties.1 However at high pressure they easily cocrystallize with the applied
solvent (water, methanol, ethanol or their mixture).2-4 A single crystals of dabco
solvates have been in situ grown in a diamond-anvil cell and their structures
determined by X-ray diffraction. Structures of unsolvated dabco salts are
governed by the NH+N hydrogen bonds, linking the dabco cations into chains.
High-pressure transforms the H-bonding pattern and the hierarchy of different
cohesion forces. It is characteristic, that above 0.5GPa pressure gradually
eliminates the NH+N homoconjugated bonds Apart from the pressure effect on
the hierarchy of hydrogen bonds, and particularly the increased role of CHO
and CHN interactions, also other structural (close packing and the volume
balance of components) as well as kinetic and dynamic effects (concentration,
solvents ratio, thermodynamic conditions as well as the rate and sequence of their
changes) can be significant for the course of crystallization. All these effects can
be useful for obtaining new compounds of desired properties.
1) M. Szafraski; A. Katrusiak J. Phys. Chem. B. 2008, 112, 6779

2) A. Olejniczak; A. Katrusiak CrystEngComm 2010, 12, 2528
3) A. Olejniczak; A. Katrusiak Cryst. Growth Des., 2011, 11, 2250
4) M. Anioa; A. Olejniczak; A. Katrusiak Cryst. Growth Des., 2014, 14, 2187
331
Nanoscopic Analysis on ROS Membrane of Bovine Retina

Ilghar Orujalipoor1, M. Erbakan2, S. Ide1,3
Dept of Nanotechnology and Nanomedicine, Hacettepe Univ., Beytepe,

Ankara, Turkey
2
Faculty of Engineering and Architecture, Dept of Biosystems Engineering,
Bozok Univ., Yozgat, Turkey
3
Faculty of Engineering, Dept of Physics Eng., Hacettepe Univ., BeytepeAnkara, Turkey
1
POSTER 32
In retina, there are two types of photoreceptor cells named cones and rods. Rod
outer segments (ROS) function as light receptors and each contains nearly 1000
intracytoplasmic membranes discs stacked in a parallel fashion which include
visual pigment protein, rhodopsin from the G protein- coupled receptor family [1].
In the present work, ROS were isolated from the bovine retinas. The fresh and
fixed ROS samples were prepared for nanoscale characterization using small
and wide angle X-ray scattering (SAXS/WAXS), as well asTransmission electron
microscopy (TEM) techniques. The distance between the intracytoplasmic discs,
3D size and the shape of rhodopsin macromolecules and the morphologies of
alpha-helix transmembranes were determined. Ab initioshape determination of
the nanodomains obtained by DAMMIN [2] simulation program showed that the
array of the GPCRs inside the membrane discs were in paracrystalline form. The
results have been compared to those within the recent publications [35].
Keyword: Retina, Photoreceptor cells, ROS, Rhodopsin
[1] H. B. Osborne, C. Sardet, and A. Helenius, Bovine rhodopsin: characterization of the
complex formed with Triton X-100., Eur. J. Biochem., vol. 44, no. 2, pp. 38390, 1974.
[2] D. Franke and D. I. Svergun, DAMMIF, a program for rapid ab-initio shape
determination in small-angle scattering, J. Appl. Crystallogr., vol. 42, no. 2, pp. 342346,
2009.
[3] D. Fotiadis, Y. Liang, S. Filipek, D. A. Saperstein, A. Engel, and K. Palczewski,
Atomic-force microscopy: Rhodopsin dimers in native disc membranes., Nature, vol.
421, no. 6919, pp. 1278, Jan. 2003.
[4] E. Malmerberg, P. H. M. Bovee-Geurts, G. Katona, X. Deupi, D. Arnlund, C.
Wickstrand, L. C. Johansson, S. Westenhoff, E. Nazarenko, G. F. X. Schertler, A. Menzel,
W. J. de Grip, and R. Neutze, Conformational activation of visual rhodopsin in native
disc membranes, Sci. Signal., vol. 8, no. 367, pp. ra26ra26, 2015.
[5] T. Rakshit, S. Senapati, S. Sinha, A. M. Whited, and P. S. H. Park, Rhodopsin forms
nanodomains in rod outer segment disc membranes of the cold-blooded Xenopus laevis,
PLoS One, vol. 10, no. 10, 2015.
332
A new high pressure phase transition in clinoferrosilite: in

situ single crystal X-ray diffraction study
Anna Pakhomova, L. Ismailova, E. Bykova, M. Bykov, T. Boffa
Ballaran, L. Dubrovinsky
Bayerisches Geoinstitute, Univ. of Bayreuth, Bayreuth, Germany
Pyroxenes, M1M2Si2O6, are one of the major constituents of

POSTER 33
the Earths upper mantle and they have an important influence
on its geological structure. A well-constrained correlation between chemical
composition, crystal structure and elastic properties of pyroxenes is hence
necessary for the modeling their behavior in the Earths interior. We report
high-pressure single-crystal X-ray diffraction (SC XRD) data of clinopyroxene
Fe end-member: clinoferrosilite (CFs). CFs transforms from a P21/c to a C2/c
phase between 1.48 and 1.75 GPa at room temperature (Hugh-Jones et al., 1996),
however little is known about its structural behavior at Earths mantle pressures.
Single crystals of CFs synthesized at 9.5 GPa and 1100 C were loaded together
with a ruby sphere pressure estimation into diamond anvil cells. Neon was used
as pressure-transmitting medium. In situ high-pressure SC XRD experiments
were performed at the synchrotron stations P02.2 at Petra III and ID09 at the
European Synchrotron Radiation Facility.
The C2/c CFs phase detected between 1.3 and 3.0 GPa undergoes anisotropic
compression up to 30 GPa according to the scheme b>ca>asin also observed
for other pyroxene. The bulk modulus of the C2/c phase and its pressure
derivative are determined to be 113(3) and 6.3(3) GPa by fitting a third-order
Birch-Murnaghan equation of state. Between 30 and 35.8 GPa, CFs transforms
into a HP-P21/c phase that undergoes compression according to the scheme
b>aasin>c . The C2/c to HP-P21/c transition is induced by rearrangement of
half of the layers of corner-sharing SiO4 tetrahedra into layers of edge-sharing
SiO6 octahedra. The new layer is topologically equivalent to the one observed in
akimotoite, the high-pressure ilmenite-type structure of MgSiO3. This observation
supports the hypothesis of a direct transition from pyroxene to akimotoite in
cold subducting slabs where the expected dissociation to spinel and stishovite is
kinetically hindered (Argusta et al., 2014).
333
Pressure- and Temperature- induced phase transition in

multiferroic perovskite EuTiO3
Paraskevas Parisiades1,2, F. Saltarelli3, A. Bussmann-Holder4,

J. Khler4, M. Mezouar1
ID27 Beamline, European Synchrotron Radiation Facility, Grenoble, France

Laboratoire Matriaux et Phnomnes Quantiques, Univ. Paris-Diderot,
Paris, France
3
Sapienza Univ. of Rome, Physics Dept., Rome, Italy
4
Max-Planck-Inst. for Solid State Research, Stuttgart, Germany
1
2
POSTER 34
Multiferroics have been a subject of intense study in the recent years, because
of the complexity of correlations between lattice, magnetism and ferroelectric
polarization, as well as their potential for practical applications such as
sensors, spintronics and nonvolatile memories. Europium titanate (EuTiO3)
is a multiferroic material with an unusually strong third-order spin-lattice
coupling, where the strongly localized 4f moments on the Eu2+ sites order
antiferromagnetically at T N = 5.5 K and are arranged in a G-type structure.
At ambient conditions, EuTiO3 adopts the cubic perovskite structure with
space group P m -3 m. On cooling it undergoes a cubic-to-tetragonal structural
transition to the I4/mcm space group. The transition temperature seems to be
controversial among different experimental techniques. In this work we report
the first application of pressure under hydrostatic conditions for this material
by exploring many different isotherm compressions up to 50 GPa. We observe
the transformation to a tetragonal phase with pressure which is fully consistent
with the temperature-induced transition. The appearance of the tetragonal
symmetry at high-P/low-T conditions is due to the rotational instability of the
TiO6 octahedra and is also present in isostructural SrTiO3. However, the absence
of multiferroic behavior for SrTiO3 is responsible for the much lower temperatures
and higher pressures of the transition in the latter material. By collecting all the
data for the antiferrodistortive transition we report a first P-T phase diagram for
EuTiO3 in the region of 0-50 GPa and 30-500 K.
Similarly with EuTiO3, we also present recent data on Eu1-xSrxTiO3 crystals. We
have tracked the high pressure structural transition for different doping levels,
and thus we add another parameter to the phase diagram of this material.
References
[1] P. Parisiades, E. Liarokapis, J. Khler, A. Bussmann-Holder, and M. Mezouar,
Phys. Rev. B 92, 064102 (2015).
334
Effects of irradiation-induced structural disordering in

zirconate pyrochlores at high pressures
Sulgiye Park1, C.L. Tracy1, F. Zhang2, C. Park3, C. Trautmann4,5,
S. Finkeldei6, M. Lang7, W.L. Mao1, R.C. Ewing1

Dept of Nuclear Engineering, Univ. of Tennessee, Knoxville,TN, USA
3
Materials Science and Technology Division, Oak Ridge National Laboratory,
Oak Ridge, TN, USA
4
HPCAT, Carnegie Inst. of Washington, Argonne, Illinois, USA
5
GSI Helmholtzzentrum fr Schwerionenforschung, Darmstadt, Germany
6
Technische Univ. Darmstadt, Darmstadt, Germany
1
2
POSTER 35
The effects of swift heavy ion irradiation-induced disordering on zirconate

compounds (A2Zr2O7where A = Sm, Er, Nd) at high pressures are investigated
using synchrotron X-ray diffraction (XRD). Irradiation experiments were
performed at the GSI Helmholtz Center with197Au ions accelerated to energy of
2.2 GeV. Angle dispersive synchrotron powder X-ray diffraction measurements
were completed at the Advanced Photon Source at Argonne National Laboratory,
where samples before and after irradiation were pressurized up to ~ 50 GPa
using diamond anvil cells. Analysis of the XRD data demonstrate that: 1)
Sm2Zr2O7and Nd2Zr2O7undergo a phase transformation from ordered pyrochlore
to a disordered defect-fluorite with swift heavy ion irradiation; 2) energetics of
disordering lower the pressure transition point in pyrochlores Sm2Zr2O7and
Nd2Zr2O7and; 3) swift heavy ion irradiation increases the pressure transition
point in a defect-fluorite Er2Zr2O7by introducing more interstitials. The effects of
disordering in different zirconate compositions under high pressure are explained
in terms of the variation in phase space with A-site cation substitution.
335
Diamond anvil cell based laser heating facility for high

temperature - high pressure research: Some recent results
Nishant N. Patel, M. Sunder, S.M. Sharma
High Pressure & Synchrotron Radiation Physics Division, Bhabha Atomic

Research Centre, Mumbai, India
A laser heated diamond anvil cell (LHDAC) facility has been

recently set up at BARC, India aimed at high pressure melting
studies and high temperature high pressure synthesis of
novel materials. The system incorporates a ytterbium fiber laser ( = 1.07 m)
for heating and spectroradiometry technique for temperature measurement.
Technical details of the experimental set up along with some recent results would
be presented.
POSTER 36
336
Synthesis of hydrides with non traditionnal stoichiometries

at high pressure
Charles Ppin1, A. Dewaele1, F. Occelli1, G. Gneste1,
M. Mezouar2, P. Dumas3, P. Loubeyre1
ESRF, Grenoble, France
3
Synchrotron SOLEIL, Gif-sur-Yvette, France
1
2
POSTER 37
Over the past 5 years numerous calculations have unveiled

a novel view on the chemical combination of hydrogen with metals under
pressure. Three remarkable trends can be identified: (i) Hydrogen stoichiometry
should drastically increase under pressure in metals, (ii) Polyhydrides with nontraditional stoichiometries should be stable under pressure, (iii) These hydrogendominant systems may become metallic at much lower pressure than for pure
hydrogen and could exhibit a high-temperature of superconductivity. A systematic
experimental study of different hydrides of low Z-elements has been undertaken.
A new synthesis method of high-quality and high-purity samples has been
developed: a metallic foil is heated at high pressure in hydrogen medium using a
YAG-laser. Using this method hydrides of iron (FeHx) were synthesized at high
pressure in a diamond anvil cell. These compounds were characterized in situ by
X-ray diffraction using synchrotron radiation light sources. Our results evidence
that the properties of the hydrides are strongly influenced by the properties of
the hydrogen sublattice and confirm the existence of a strong analogy between
hydrides with a high hydrogen content and pure hydrogen. Moreover, we
confirmed the stability of new polyhydrides with non-traditional stoichiometries
under high pressure through the synthesis of new iron hydrides FeH2 and FeH3.
Another study on LiH strengthened these results as we observed the formation of
LiH2 and LiH6 when compressing pure lithium hydride LiH above 160 GPa.
337
Revisiting the pressure induced transformations of Benzene:

compression at low temperature and the use of a hydrostatic
pressure transmitting medium
Thomas Plisson, P. Loubeyre
Benzene is a molecule of fundamental interest. It exhibits an

aromatic structure, and could be a pathway to the formation
of graphane, the hydrogenated equivalent of graphene. Recently, ab-initio
simulations have been performed to investigate the stability of benzene allotropes
at high pressure [1]. They predict that graphane is more stable than benzene and
that benzene should eventually become metallic around 200 GPa. Furthermore,
in the recent investigations of hydrides, it has been pointed out that organic
molecules could be suitable systems to host high pressure superconductivity [2].
Under pressure at ambient temperature, benzene has been observed to amorphize
at 40 GPa. This transformation has been studied in details by the Lens group [3]
and is explained by the local bridging of benzene molecules mediated by thermal
vibrations. It has been shown that heating and visible laser illumination favors
amorphization, making Raman spectroscopy difficult. This amorphization could
prevent the system from becoming metallic at high pressure. However, as pointed
out by [1], low temperature should delay the amorphization, possibly enough to
reach the metallic transition. To our knowledge, the low temperature and high
pressure part of the phase diagram has never been studied.
We are currently investigating the high pressure and low temperature phase
diagram of benzene compressed in a diamond anvil cell. We have set up an
infrared Raman spectroscopy bench at 1064 nm adapted for this project. Raman
data will be completed by an infrared absorption experiment at synchrotron
Soleil. We hope to confirm the amorphization mechanism by studying the
influence of a pressure transmitting medium and to measure the crystalline
properties of benzene over an extended pressure range.
POSTER 38
[1] X.D. Wen, R. Hoffmann and N.W. Ashcroft, Journ. Am. Chem. Soc., 133, 9023
(2011).
[2] A.P. Drozdov et al, Nature, 525, 73-76 (2015).
[3] L. Ciabini et al, Nature, 6, 39 (2007).
338
Neutron studies under extreme magnetic fields

Karel Prokes, B. Lake, P. Smeibidl, O. Prokhnenko
Helmholtz-Zentrum Berlin, Berlin, Germany
Neutron diffraction experiments play a crucial role in solving

various physical problems. Due to its interaction with both,
nuclei and open electron shells, neutrons provide information
POSTER 39
on the crystal and magnetic structures. As the magnetic state
often depends on external conditions, studies of a magnetic state as a function of
external variables are very common. These include for instance the determination
of magnetic structures and phase transitions as a function of temperature,
magnetic field, pressure and other thermodynamical conditions like electric field.
Phase diagrams are constructed. Neutron beam is a weak probe that is able to
penetrate certain materials rather easily without substantial loss of intensity. This
enables construction of complicated sample environments and combination of
low temperatures with high magnetic fields and pressures, leading to truly multiextreme conditions.
In the contribution we present recent HFM-EXED project that combines
dedicated neutron scattering instrument with a horizontal solenoid magnet with
tapered cones. This project was recently realized at Helmholtz-Zentrum Berlin in
collaboration with the National High Magnetic Field Laboratory of Florida State
University, USA. The magnet utilizes hybrid (resistive insert and superconducting
outsert) technology and is capable to produce static magnetic field of 26-32 T,
depending on the power that is between 4 and 8 MW. The dedicated instrument
is of time-of-flight (TOF) type and optimized for diffraction at restricted
geometrical conditions. In the contribution we describe all major components of
the facility and discuss few recent scientific experiments performed using this
facility.
339
The effect of nickel on the strength of hcp-iron at highpressures

Mary M. Reagan1, A.E. Gleason2, W.L. Mao1,3

Shock and Detonation Physics, LANL, Los Alamos, NM, USA
3
Photon Science, SLAC National Accelerator Laboratory, Menlo Park, CA, USA
1
2
POSTER 40
Hydrostatic nuclear resonance inelastic x-ray scattering coupled

with non-hydrostatic radial x-ray diffraction measurements can
be used to determine the shear strength of Fe-bearing materials at core pressures.
Using the Singh et al. formalism (2006), the bulk shear strength (t) of a material
is related to its shear modulus(G) and to the average differential strain () over
all measured lattice planes (hkl) by t = 6G. We followed an existing framework
(Gleason & Mao, 2013) and extend the strength determinations to investigate
the effect of nickel on the strength of iron at high pressure. We collected radial
X-ray diffraction data on Fe90Ni10 and Fe80Ni20 using a panoramic diamond anvil
cell with an X-ray transparent gasket to 60 GPa. This data was combined with
existing NRIXS data (Lin 2003) to calculate the strength of these compounds.
The strength of these iron-nickel alloys can be extrapolated to deep earth
pressures to give a new constraint on the state of the inner core. Gaining a better
understanding of the strength of iron and its alloys at high pressures can shed
light on the strength of the inner core and provide insight into the deformation
processes operating in the most remote region of our planet.
340
Comparative HP/HT elasticity measurements on singlecrystals of hydrous/iron-bearing ringwoodite

Kirsten Schulze1, H. Marquardt1, T. Kawazoe1, A. Kurnosov1,
M. Koch-Mller2, T. Boffa Ballaran1
1
2

Deutsches Geoforschungszentrum (GFZ), Potsdam, Germany
POSTER 41
Olivine and its high-pressure polymorphs wadsleyite and

ringwoodite are the most abundant minerals in the upper
mantle. The elastic tensor of ringwoodite is not only dependent on the pressure
and temperature conditions but also on the Fe/Mg ratio and the hydration
state. Differences in experimental set up and sample characterisation between
published studies make it difficult to reliably quantify the effect of these chemical
variations. We present first results of internally consistent single-crystal elasticity
measurements of chemically diverse ringwoodite crystals at high pressure.
Single-crystals of ringwoodite were synthesised in multi-anvil experiments with
chemical compositions ranging from Mg2SiO4 to (Mg0.89,Fe0.11)2SiO4 and about
0.4 wt.%H20 to more than 2 wt.%H20. Four ringwoodite single-crystals with
different compositions were oriented, double-side polished and cut into quartercircles with a FEI Scios Focused Ion Beam (FIB). To ensure the same temperature
and pressure conditions for all samples, all four samples were loaded in the
pressure chamber of one diamond anvil cell (DAC), ruby spheres were added as a
pressure marker. We perform single-crystal x-ray diffraction (XRD) and Brillouin
spectroscopy measurements to determine the effect of Fe and OH-defects on the
elastic constants and densities at high pressure. XRD at 1 GPa showed that the
incorporation of OH-defects equivalent to ~1.8 wt.%H2O in Fo90 ringwoodite
leads to an increase in the unit cell volume of ~ 2.8 3. A decrease in unit cell
volume of ~ 3 3 is observed in Mg-endmember ringwoodite compared to a Fo90
ringwoodite with similar water content. Brillouin spectroscopy at 1 GPa shows
decreased phonon frequency shifts with increasing hydration in Fo90 ringwoodite
and highest frequency shifts in the Mg-endmember.
341
The evolution of interatomic and intermolecular interactions

and polymorphism of melamine at high pressure
Hannah Shelton1, P. Dera1, Y. Meng2, S. Tkachev3
Hawaii Inst. of Geophysics and Planetology, Univ. of Hawaii at Mnoa,

Honolulu, HI, USA
2
High Pressure Collaborative Access Team, Carnegie Inst. of Washington,
Advanced Photon Source, Argonne National Laboratory, IL, USA
3
Center for Advanced Radiation Sources, Univ. of Chicago, Argonne
National Laboratory, Chicago, IL, USA
1
POSTER 42
Melamine (C3H6N6; 1,3,5-triazine-2,4,6-triamine) is an aromatic ring molecule,

with carbon and nitrogen atoms forming the ring body, and amine groups bonded
to each carbon. Melamine is widely used to produce laminate products, adhesives,
and flame retardants. However, melamine has a very similar structure to several
well known explosives, including triamino-trinitrobenzene (TATB). Additionally,
melamine may be a precursor in the synthesis of superhard carbon-nitrides, such
as -C3N4.In its solid form, individual melamine molecules are linked to others
via eight N-H hydrogen bonds. The superstructure of melamine forms corrugated
sheets of individual melamine molecules, where kinked planes of molecules are
stacked on top of one another.Several previous high pressure x-ray diffraction
and Raman spectroscopy studies have claimed that melamine undergoes two or
more phase transformation below 25 GPa. Our single crystal data demonstrate
that melamine retains the ambient, monoclinic structure up to almost 40 GPa. At
37 GPa, the unit cell volume has decreased by more than a factor of two without
significant chance in the molecular geometry, as the hydrogen bond distances
between molecular units decrease. A phase transition to a triclinic structure,
different than the one previously suggested, was found around 40 GPa. Examining
the effect hydrogen bonds have on melamines structure will allow it to be better
utilized as a chemical feedstock and analog for related compounds.
342
High-pressure behavior of Mg2Fe2O5
Nicki C. Siersch1, T. Boffa Ballaran1, L. Uenver-Thiele2,

A.B. Woodland2

Inst. fr Geowissenschaften, Goethe-Univ. Frankfurt, Frankfurt am Main,
Germany
1
2
POSTER 43
The compressibility and structural behavior at high pressures

of the novel Mg2Fe2O5 oxide has been investigated in this study.
In-situ single-crystal X-ray diffraction was performed in a diamond anvil cell up
to pressures of 17 GPa. The bulk compressibility of Mg2Fe2O5 has been described
using a second-order Birch-Murnaghan equation of state (BM2 EoS) with V0 =
352.4(5) 3 and K0 = 171(5) GPa. Three linear BM2 EoS were used to describe the
axial compressibility of Mg2Fe2O5 which was found to be highly anisotropic. The
a and b lattice parameter have a very similar compressibility with a0 = 2.8919(15)
, Ma = 568(20) GPa and b0 = 9.7395(50) , Mb = 570(20) GPa, respectively.
The c-axis is the most compressible direction as indicated by the smaller linear
modulus (c0 = 12.5225(18) and Mc = 400(32) GPa). The Mg2Fe2O5 structure
consists of edge-sharing octahedra alternating with layers of trigonal prisms. The
compression behavior of the O atoms in the M1 and M2 octahedra and the M3
prisms depend on their location in either an edge-sharing environment which
makes them stiffer or a corner-sharing environment which gives them more
freedom to move and compress. The main compression mechanism consists
of a tilting of the M2-O1-M2 angle which decreases with increasing pressure.
Above 4 GPa, however, this angle appears to stiffen more rapidly, likely due to
the repulsion of the O3 atoms of the two adjacent M2 octahedra. Mg2Fe2O5
has recently been added to the list of stable endmembers of phases with M4O5
stoichiometry which makes it relevant for the expected bulk composition of the
Earths upper mantle and transition zone. To be able to perform thermodynamic
activity-composition models it is crucial to know the exact elastic parameters of
each individual endmember which so far only have been investigated for Fe4O5.
343
Novel Radionuclide Wasteforms Prepared Under Pressure

Emily Siska
Univ. of Nevada Las Vegas, Las Vegas, NV, USA
Currently, the most widely used waste form for nuclear waste
is borosilicate glass. Although glass and ceramic waste forms
have proven to immobilize many radionuclides; they are not
POSTER 44
ideal for certain radionuclides including I2, Kr, Tc and actinides.
These nuclear waste products have long half-lives and have particularly harmful
health and environmental effects. There is a need to design new waste forms
that can immobilize these problematic radionuclides and reliably store them
for thousands and in some cases millions of years. Minerals, such as zeolites
are composed of Earth-abundant, inexpensive, low toxicity elements that show
potential as wasteforms. Lattice distortions and vibrations brought on by pressure
and temperature can make the structure of these normally rigid frameworks
flexible enough to allow for the diffusion of small molecules/ions. This study
focuses on the potential of silicious sodalite to be a wasteform. Compression
of silica-sodalite was performed in different media in hopes of learning the
behavior and capabilities of the structure and how to possibly improve it for waste
immobilization. Also, using General Utility Lattice Program (GULP) we predict
pressure dependent changes to the structures.
344
A temperature-induced orderdisorder phase transition in a

4-substituted 4,2:6,4-terpyridine
Sebastin Surez1,2, J. Granifo3, M. Westermeyer3,
M. Riquelme3, R. Gavio4, E. Halac2, R. Baggio2
Dep. de Qumica Inorgnica, Analtica y Qumica Fsica, INQUIMAECONICET, Facultad de Ciencias Exactas y Naturales, Univ. de Buenos Aires,
Buenos Aires, Argentina
POSTER 45
2
Gerencia de Investigacin y Aplicaciones, Centro Atmico Constituyentes,
Comisin Nacional de Energa Atmica, Buenos Aires, Argentina
3
Dep. de Ciencias Qumicas y Recursos Naturales, Facultad de Ingeniera y Ciencias, Univ. de La
Frontera, Temuco, Chile
4
Inst. de Qumica, Univ. Nacional Autnoma de Mxico, Mxico City,Mxico
1
Crystals of 4-(isoquinolin-4-yl)-4,2:6,4-terpyridine (iqtp), C24H16N4, grown

from an ethanol solution undergo a reversible first-order, single-crystal to singlecrystal phase transition at Tc in the range 273-275 (2) K, from a disordered
higher-temperature phase (Form I) in SG. P21/c, with one single molecule in
the asymmetric unit, to an ordered lower-temperature one (Form II) in SG.
P21/n, with two independent molecules. There is a group:subgroup relationship
linking I-II, due to cell doubling and the disappearance of a number of symmetry
operations. In addition to X-ray diffraction, the transition has been monitored by
Raman spectroscopy and differential scanning calorimetry (disclosing an enthalpy
change of 0.72(6) kJ/mol). Variations of the unit-cell parameters with temperature
between 170 and 293K are presented. The evolution of diffraction spots in
the vicinity of the transition temperature shows coexistence of both phases,
confirming the first order character of the transition. Structural details of both
phases are analyzed and the intermolecular interactions compared in order to
investigate the mechanism of the phase transition. A three-dimensional Hirshfeld
surface analysis was performed to corroborate the significant changes into the
intermolecular features.
345
NRIXS method at high pressure and applications in

geoscience
Hong Yang1, J.F. Lin1,2, N. Dauphas3, J. Zhao4, W. Bi4
Center for High Pressure Science and Technology Advanced Research

(HPSTAR), Shanghai, China
2
Dept of Geological Sciences, The Univ. of Texas at Austin, Austin, TX, USA
3
Origins Laboratory, The Univ. of Chicago, Chicago, IL, USA
4
Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA
1
POSTER 46
Nuclear Resonant Inelastic X-ray Scattering(NRIXS) is a powerful technique in

probing vibrational information of solids. It directly measures the phonon density
of states(PDOS) of Mossbauer isotopes in lattice, which can be used to derive
very rich information including the Debye sound velocities and force constants.
Combining with DAC technique, we can in-situ probe the high pressure
properties of Earth relevant materials and study various geologic processes in
Earths interior. The sound velocities of minerals at high pressure are of great
importance in modeling the mineralogy of the deep Earth and force constants
control the scale of isotope fractionation between minerals. In the poster, I will
present some high pressure NRIXS experimental results collected at 3ID-B of the
Advanced Photon Source and discuss the geological implications.
346
Electrical and thermal transport properties of iron alloy at

earths core condition
Chengwei Zhang1, J.-F. Lin1,2
Center for High Pressure Science and Technology Advanced Research,

Shanghai, China
2
Dept Geological Sciences, Jackson School of Geosciences, The Univ. of Texas
at Austin, Austin, TX, USA
1
POSTER 47
Throughout earth history, energy from the core has been

transferred to upper layers in the form of heat conduction. When comparing the
energy consumed and given energy sources, we found there is an imbalance which
could lead to the deficiency of sustaining the geodynamo. To give a explanation
of this phenomenon, we measured the electrical resistivity of Fe3C alloy at high
pressure and want to provide a new value of heat conductivity of earth core.
We found the resistivity of iron-carbon alloy is much lower than the other iron
alloy with light element impurities, which suggests that carbon has the effect
of lowering down the conductivity of iron alloy in earth core. This observation
may renew the present recognition of heat conduction in core, resulting that
geodynamo can be powered by the present energy sources without additional.
347
High pressure crystallography at the Partnership for

eXtreme Xtallography program
Dongzhou Zhang, Przemyslaw K. Dera
Univ. of Hawaii at Manoa, Honolulu, HI, USA
The Partnership for eXtreme Xtallography (PX^2) program is a

research initiative focusing on high pressure diamond anvil cell
POSTER 48
research, supported by the Consortium for Materials Properties
Research in Earth Sciences (COMPRES). PX^2 is a collaboration between the
University of Hawaii at Manoa and GeoSoilEnviroCARS (GSECARS), located at
the Advanced Photon Source (APS) experimental station 13-BM-C. This beamline
provides focused X-rays at two fixed energies: 15 and 29 keV, and a unique 6-circle
heavy duty diffractometer, optimized for a variety of advanced crystallography
experiments including interface studies, powder and single crystal structure
determination, equation of state studies and thermal diffuse scattering. Multiple
auxiliary experimental capabilities, including online ruby fluorescence pressure
determination, Raman spectroscopy, and remotely-controlled resistive heating for
diamond anvil cell, are available for high pressure research. Diffraction studies at
P-T conditions of more than100 GPa and 1000 K have been carried out at PX^2,
and several materials of interest to Earths deep interior have been studied. These
new capabilities are available to all researchers interested in studying deep earth
materials through the APS General User Proposal system.
348
Additional Participants
349
Seyfettin Ayhan
Kenneth Freeman
Richard Gaal
Karl Hope
Tamara Koch
Sumit Konar
Marjorie Ladd Parada
Wendy Mao
Martha Pamato
350
Michelangelo Polisi
Patrick Rosa
Sandro Scandolo
Demetrio Scelta
Melissa Sims
Dean Smith
Andrew Thomson
Peter Wood
351
352
Presenting author index

A
Abdurakhimov, Bekhzodjon 301

Angel, Ross J. 39, 90, 117, 281, 283
Anzolini, Chiara 302
Katrusiak, Andrzej 234

Kumar, S. Madan 318
Bebiano, Suse S. 303

Berryman, Eleanor 304
Biedermann, Nicole 305
Bove, Livia E. 140
Brant, William R. 306
Brooks, Nick 180
Lampropoulos, Christos 319

Laniel, Dominique 295
Lanza, Arianna 320
Li, Ching-Chien 321
LimaJr., J. Alves 322
Liu, Xiaojiao 323
Lotti, Paolo 324, 325
Cairns, Andrew B. 290, 307

Chapman, Karena W. 213, 270
Childs, Christian 296, 308
Chitnis, Abhishek 309
Coates, Chloe S. 310
Comboni, Davide 287, 311
Connor, Lauren Evelyn 289, 312
Machon, Denis 225

Marciniak, Jdrzej 326
Martok, Roman 241
Maynard-Casely, Helen 159
Mazzucchelli, Mattia Luca 327
McMahon, Malcolm 19, 61
McMonagle, Charlie 328
Mndez, Alba San Jos 329
Montisci, Fabio 330
D
Deemyad, Shanti 313
Devarapalli, Ramesh 297
Direm, Amani 314
Dutta, Rajkrishna 315
Fabbiani, Francesca P.A. 189
Pakhomova, Anna 333

Parise, John B. 256
Parisiades, Paraskevas 334
Park, Sulgiye 294, 335
Parsons, Simon 105, 202
Pascarelli, Sakura 127, 171
Patel, Nishant N. 336
Ppin, Charles 337
Plisson, Thomas 338
Prokes, Karel 339
G
Guka, Piotr A. 288
Guthrie, Malcolm 72
H
Hudspeth, Jessica M. 317
Hu, Yi 316
Olejniczak, Anna 331

Orujalipoor, Ilghar 332
Irifune, Tetsuo 51
353
R
Reagan, Mary M. 340
Ritter, Xenia 292
S
Sanloup, Chrystle 246
Schulze, Kirsten 298, 341
Shelton, Hannah 291, 342
Siersch, Nicki C. 343
Siska, Emily 344
Surez, Sebastin 345
W
Woodall, Christopher H. 293
Y
Yang, Hong 346
Z
Zhang, Chengwei 347
Zhang, Dongzhou 348
354

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49th Course

Erice, Italy 27 May -5 June 2016

It is also sponsored by:

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 48th Course, 27 May - 5 June 2016

Saturday, 28 May 2016

11:45-12:30 Tetsuo Irifune

15.15-16:00 Malcolm Guthrie

Workshops introduction + sign up

18:00-20:00 Free time

Welcome buffet & Folk show

Erice International School of Crystallography 48th Course, 27 May - 5 June 2016

Sunday, 29 May 2016

Short (2-3 mins) presentations of poster (odd numbers)

Demo: Angel (EosFit)

16:30-18:00 Bruker - pure demo

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Monday, 30 May 2016

Erice International School of Crystallography 48th Course, 27 May - 5 June 2016

Tuesday, 31 May 2016

14:30-16:00 ABSORB - demo

16:30-18:00 EXAFS - follow me

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Wednesday, 1 June 2016

11:45-12:30 Workshop: communication of high-pressure crystallography

Short (2-3 mins) presentations of poster (even numbers)

Bruker - pure demo

16:30-18:00 PDF - demo

Erice International School of Crystallography 48th Course, 27 May - 5 June 2016

Thursday, 2 June 2016

EXCURSION 2 (buffet dinner at Segesta)

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Friday, 3 June 2016

Selected participants talks

10:30-11:00 Coffee break

Selected participants talks

16:30-18:00 EosFit - follow-me

Saturday, 4 June 2016

Selected participants talks

Future challenges round table

Future challenges panel discussion

Closing remarks and Awards

18:00-20:00 Free time

Good Bye buffet dinner

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Invited Speakers Contributions

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

High Pressure Crystallography An Introduction

School of Physics & Astronomy, The Univ. of Edinburgh, Edinburgh, UK

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

containing materials32,33, magnetism34,35 and phonons36, or to make high real-space resolution

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

X-Ray Powder Diffraction

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

ADXRD techniques revolutionised high-pressure crystallography19. They used monochromatic

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016

Erice International School of Crystallography 49th Course, 27 May - 5 June 2016