X-ray Absorption

Spectroscopy
XAS
 X-ray absorption spectroscopy (XAS) is
a widely-used technique for determining
the local geometric and/or electronic
structure of matter
Samples can be in the gas-phase,
solution, or condensed matter (ie. solids).
Working

When the x-rays hit a sample, the oscillating electric field

of the electromagnetic radiation interacts with the
electrons bound in an atom, either the radiation will be
scattered by these electrons, or absorbed and excite the
electrons.
ln ( I0 / I ) = x
is the linear absorption coefficient, which depends on the types of atoms and the
density of the material.
 At certain energies where the absorption increases
drastically, and gives rise to an absorption edge.
Each such edge occurs when the energy of the incident
photons is just sufficient to cause excitation of a core
electron of the absorbing atom to a continuum state, i.e.
to produce a photoelectron.
Thus, the energies of the absorbed radiation at these
edges correspond to the binding energies of electrons in
the K, L, M, etc, shells of the absorbing elements.
 When the photoelectron leaves the absorbing atom, its
wave is backscattered by the neighboring atoms.

The figure shows the sudden increase in the x-ray absorption of the platinum Pt LIII edge in
K2[Pt(CN)4] (Potassium tetracyanoplatinate) with increasing photon energy. The maxima and
minima after the edge correspond to the constructive and destructive interference between the
outgoing photoelectron wave and backscattered wave.
 An x-ray absorption spectrum is generally divided into 4 sections:

1. pre-edge (E < E0)

2. x-ray Absorption Near Edge Structure (XANES), where

the energy of the incident x-ray beam is E = E0 10 eV

3. Near Edge x-ray Absorption Fine Structure (NEXAFS), in

the region between 10 eV up to 50 eV above the edge

4. Extended x-ray Absorption Fine Structure (EXAFS), which

starts approximately from 50 eV and continues up to 1000
eV above the edge.
 The minor features in the pre-edge region are usually
due to the electron transitions from the core level to the
higher unfilled or half-filled orbitals (e.g, s p, or p
d).

In the XANES region, transitions of core electrons to

non-bound levels with close energy occur. Because of
the high probability of such transition, a sudden raise of
absorption is observed.
 In NEXAFS, the ejected photoelectrons have low kinetic
energy (E-E0 is small) and experience strong multiple
scattering by the first and even higher coordinating
shells.

Final Density of states, the transition probability,

resonance and many body effect.
 In the EXAFS region, the photoelectrons
have high kinetic energy (E-E0 is large),
and single scattering by the nearest
neighboring atoms normally dominates.

Local Coordination and interatomic distance

 EXAFS

In the EXAFS process, the excited electron wavefunction (wavelength )

propagates away from the atom at which photon absorption occurs, and is
backscattered from surrounding atoms. The interatomic distance is r.
 EXAFS
EXAFS gives a spherical average of information
in a shell around an absorbing atom.
The angular variation of the EXAFS intensity is
one of the best methods of identifying an
adsorption site
The form of the backscattering amplitude
depends on atomic number, helps to determine
which atoms in a compound are nearest
neighbors.
 When the photon energy equals the binding energy of the electron in a core level, a
strong increase in absorption is seen, which is known as the absorption edge.

The absorbed photon gives its energy to a photoelectron that propagates as a wave.

In a molecule or solid, part of this photoelectron wave may be backscattered from

neighboring atoms, the backscattered wave interfering constructively or
destructively with the outgoing wave.

Thus one gets a spectrum of absorption as a function of photon energy that contains
wiggles (EXAFS) superimposed on a smooth background.

The amplitude of the EXAFS wiggles depends on the number of neighbors, the
strengh of their scattering and the static and dynamic disorder in their position.

The frequency of the EXAFS wiggles depends on the wavevector k of the

photoelectrons (related to their kinetic energy) and the distance to neighboring atoms.

The frequency is inversely related to the nearest neighbor separation, with a short
distance giving widely spaced wiggles and vice versa.
The effect of coordination number and nearest-neighbour distance on
the form of the EXAFS spectrum

Shorter bonds give rise to

larger spaced oscillations
(compare R1 and R2).
Whilst an increase in
coordination number gives a
larger amplitude (compare the
traces for a two-coordinate and
a six-coordinate species in C)
Shorter bonds are
characterized by larger-spaced
EXAFS oscillations,
EXAFS amplitude increases
with the number of nearest-
neighbour atoms
 NEXAFS
NEXAFS is a powerful technique for probing the
structure of molecules on surfaces
Observation of intense resonances near the X-
ray absorption edge can indicate the type of
bonding
The intensity resonances vary with angle of the
specimen can give the molecular orientation,
which is precise to within a few degrees
The energies of resonances allow to estimate
the intra molecular bond length, often to within
0.05
 As the photoelectron wavefunction is
strongly dependent on the form of the
potential around the absorber, NEXAFS
can be used to investigate the oxidation
state of the absorber and its coordination
geometry- the position of the absorption
edge changes as the charge on the
absorber changes
 When an electron scatters from an atom,
its phase is changed, so that the reflected
wave is not in phase with the incoming
wave.
This changes the interference pattern
Knowledge of this phase shift is the key to
getting precise bond lengths
Chemical Shifts and PeEdge Features
The absorption edge occurs when the photon energy is
equal to the binding energy of an electron core level.
Shifts in the position of the edge are caused by small
differences in the chemical environment
Features may be seen before the absorption edge, most
obviously in transition metals and their compounds.
These small peaks are characteristic of local
coordination (octahedral, tetrahedral ): their intensity
increases with oxidation state.
Peak A is identified as a pi resonance,
arising from transitions from the C 1s
state to the unfilled pi* molecular
orbital.
Peak B comes from CO impurity.
Peaks C and D are transitions to Sigma
shape resonances that lie in the plane
of the molecule.
The variation of intensity of the pi and
sigma resonances with polarization
angle gives the molecular orientation,
each peak being maximized when the
polarization vector E lies along the
direction of the orbital.
Shanghai Synchrotron Radiation Laboratory.