Computer Modeling in Inorganic Crystallography

Computer Modelling in Inorganic Crystallography

First Edition

C.R.A. Catlow

The Royal Institution of Great Britain, 21 Albemarle Street, London W1X 4BS, UK

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Table of Contents

Cover image

Title page

Copyright page

Preface

Contributors

1: Need and Scope of Modelling Techniques

1 INTRODUCTION

2 TYPES OF METHODOLOGY

3 ENERGY MINIMIZATION

4 MOLECULAR DYNAMICS (MD)

5 MONTE CARLO TECHNIQUES

6 CASE STUDIES

7 SUMMARY AND CONCLUSIONS

Section One: Methodologies

2: Bond Valence Methods

1 INTRODUCTION

2 THE CHEMICAL BOND MODEL FOR INORGANIC SOLIDS

3 DETERMINING THE STRUCTURE

4 REFINING THE GEOMETRY

5 SUMMARY

3: Lattice Energy and Free Energy Minimization Techniques

1 INTRODUCTION

2 POTENTIAL MODELS

3 PARAMETERIZATION OF POTENTIALS

4 LATTICE ENERGY MINIMIZATION

5 FREE ENERGY MINIMIZATION

6 APPLICATIONS

7 CONCLUSIONS

4: Molecular Dynamics Methods

1 INTRODUCTION

2 ALGORITHMS

3 CALCULATION OF THE POTENTIAL ENERGY AND FORCES*

4 INTEGRATION OF THE EQUATIONS OF MOTION

5 EVALUATION OF PROPERTIES AT RUN TIME

6 FURTHER ELABORATION OF THE PRIMARY DATA

7 OTHER ENSEMBLES

8 SOME EXAMPLES OF APPLICATIONS

ACKNOWLEDGEMENT

5: Simulated Annealing and Structure Solution

1 INTRODUCTION

2 MULTIDIMENSIONAL ENERGY SURFACES

3 SIMULATED ANNEALING

4 SIMULATION OF STRUCTURE

5 NON-FRAMEWORK CATION LOCATION IN ALUMINOSILICATE ZEOLITES

6 SIMULATED ANNEALING APPLICATIONS

7 MOLECULAR CRYSTALS

8 CONCLUSIONS

ACKNOWLEDGEMENTS

CRYSTAL STRUCTURE IMAGES LIBRARY

6: Reverse Monte Carlo Methods for Structural Modelling

1 INTRODUCTION

2 RMC METHOD

3 APPLICATIONS

4 FUTURE DEVELOPMENTS

7: Defects, Surfaces and Interfaces

1 INTRODUCTION

2 BULK DEFECTS

3 SURFACES AND OTHER INTERFACES

4 DEFECTS AND INTERFACES

5 CONCLUSIONS

8: Electronic Structure

1 INTRODUCTION

2 PERIODIC QUANTUM THEORY

3 COMPLEX PHYSICAL STRUCTURES

4 COMPLEX ELECTRONIC STRUCTURE – TRANSITION METAL OXIDES

5 CONCLUSIONS

Section Two: Case Studies

9: Silicates and Microporous Materials

I INTRODUCTION

2 ZEOLITIC MATERIALS

3 MANTLE-FORMING MINERALS

4 SUMMARY

10: High-TC Superconductors

1 INTRODUCTION

2 THEORETICAL METHODS

3 CRYSTAL STRUCTURES

4 DEFECT CHEMISTRY OF La2CuO4 AND Nd2CuO4

5 Y–Ba–Cu–O SYSTEMS: YBa2Cu3O7–X

6 La2CaCu2O6, La2SrCu2O6 AND RELATED COMPOUNDS

7 Sr–Ca–Cu–O SUPERCONDUCTORS

8 CONCLUSIONS

APPENDIX KRÖGER–VINK NOTATION

11: Molecular Crystals

1 THE CONTRAST BETWEEN MOLECULAR AND IONIC SOLIDS

2 THERMAL EFFECTS AND IMPLICATIONS FOR TARGET ACCURACY

3 MOLECULAR STRUCTURES WITHIN CRYSTALS

4 DEVELOPMENTS IN MODEL INTERMOLECULAR POTENTIALS

5 DEVELOPMENTS IN CRYSTAL STRUCTURE PREDICTION METHODS

6 OUTLOOK

ACKNOWLEDGEMENTS

12: Amorphous Solids

1 INTRODUCTION

2 TECHNIQUES

3 APPLICATIONS

4 CONCLUSIONS

ACKNOWLEDGEMENTS

Index

Color Plate

Copyright

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Preface

C.R.A. Catlow

Computer modelling techniques are now having a major impact on several key areas of contemporary science. Moreover, the range and scope of the techniques are constantly expanding due to development in methodologies and algorithms and to the continuing and dramatic expansion in the capabilities of the hardware. In atomistic modelling, one of the most basic and enduring class of applications concerns the modelling (and increasingly the prediction) of structures. Such methods may be used as an aid to analysis of experimental data, and more ambitiously as design tools in the development of new materials. The present book focuses on applications to inorganic materials. Its theme is the use of modelling methods as tools in the development of atomistic structural models for the bulk, defect and surface structures of crystalline inorganic solids, although discussion of molecular and amorphous materials is included. The aim is to show the applicability of these techniques to real, complex problems of importance in current experimental studies of inorganic materials.

The book has profited from input and advice from many groups and individuals. But I am especially grateful to Professor A.M. Stoneham, Professor Sir John Meurig Thomas and Professor A.K. Cheetham for discussion during many years on the applications of modelling methods in the science of inorganic materials.

April, 1996

Contributors

N.L. Allan   School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK

R.G. Bell   The Royal Institution of Great Britain, 21 Albemarle Street, London W1X 4BS, UK

I.D. Brown   Brockhouse Institute for Material Research, McMaster University, Hamilton, Ontario, Canada L8S 4 M1

C.R.A. Catlow   The Royal Institution of Great Britain, 21 Albemarle Street, London W1X 4BS, UK

C.M. Freeman   Molecular Simulations Inc., 9685 Scranton Road, San Diego, CA 92121-3752, USA

A.M. Gorman   Molecular Simulations Inc., 9685 Scranton Road, San Diego, CA 92121-3752, USA

J.H. Harding   Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UK

N.M. Harrison   CLRC, Daresbury Laboratory, Warrington, Cheshire WA4 4 AD, UK

R.A. Jackson   Department of Chemistry, University of Keele, Keele, Staffs ST5 5BG, UK

P.W.M. Jacobs   Department of Chemistry, The University of Western Ontario, London, Canada N6A 5B7

W.C. Mackrodt   School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK

R.L. McGreevy   Studsvik Neutron Research Laboratory, Uppsala University, S-61182 Nyköping, Sweden

J.M. Newsam   Molecular Simulations Inc., 9685 Scranton Road, San Diego, CA 92121-3752, USA

S.C. Parker   School of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK

G.D. Price   Department of Geological Sciences, University College London, Gower Street, London WC1E 6BT, UK

S.L. Price   Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK

Z.A. Rycerz   Department of Chemistry, The University of Western Ontario, London, Canada N6A 5B7

P. Tschaufeser   School of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK

B. Vessal   1830 Redwing Street, San Marcos, CA 92069, USA

A. Wall   School of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK

G.W. Watson   School of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK

1

Need and Scope of Modelling Techniques

C.R.A. Catlow

1 INTRODUCTION

Atomistic computer modelling techniques are now used extensively in a wide range of fields in both biological and physical sciences (see e.g. van Gunsteren and Berendsen, 1990; Allen and Tildesley, 1987; Catlow et al., 1989). Using these methods we are increasingly able to develop and explore models of the structures, energetics and dynamics of complex molecules and materials; and indeed computer modelling methods are now applied together with experiment in constructing models and solving structural problems. There have been many successes in the applications of these techniques to biological systems; an important and relevant class of examples is the concerted use in protein structural studies of molecular modelling and least squares refinements in solving protein structures (e.g. Brunger and Rice, 1995). The incentive for their application to the structural chemistry of inorganic systems is equally strong, as the study of these materials is increasingly concerned with complex structures, for example zeolites (and other microporous solids), high temperature superconductors and other ternary and quaternary oxides. As this book will show, computational methods now play a central rôle in modelling these and other topical inorganic materials.

To what specific types of problem do we wish to apply computational methods in structural inorganic chemistry? The first and most obvious are in modelling crystal structures. Computational techniques are now able to refine and reproduce accurately the crystal structures of a diverse range of inorganic systems; examples will be given in Chapters 3, 5, 9 and 10. Such methods are being used to assist the refinement of crystal structure data; the real challenge in this field is now to develop procedures for predicting structures. Considerable success has been enjoyed for several years by simple but effective procedures based on Pauling’s rules for generating approximate structural models of crystals. Such approaches will be described in Chapter 2. Computational methods for generating structures with little prior knowledge are developing fast and will be reviewed in Chapter 5; and the goal of automated prediction of inorganic crystal structures is now in sight.

There is perhaps an even greater incentive for the development of methods for modelling amorphous structures owing to the well-known difficulties in the determination of accurate and unambiguous atomistic structures for non-crystalline solids from experimental data alone. Chapter 12 will concentrate on this aspect of structural modelling. Inorganic surface chemistry is a field of growing importance and activity. Simulation techniques again have a unique role in developing models of structures and energies as discussed in Chapter 7, where we will stress the application of these methods to complex systems including ternary oxides.

One of the oldest and most successful fields of application of simulation techniques in solid state science concerns the study of defects in solids which, of course, influence many key properties including transport, reactivity and mechanical behaviour. Simulation techniques have been used with success for over 20 years in calculating formulation and migration energies of defects in solids. An account of the present state of the art is given in Chapter 7.

Dynamical processes in solids, including vibrational properties and atomic diffusion are of obvious interest and importance, not only in a crystallographic context but in broader aspects of materials science. Chapter 4 therefore focuses on the application of molecular dynamics simulation techniques in the explicit modelling of the atomic dynamics of solids.

One of the most exciting recent developments in the fields of computational chemistry and physics has been the increasing scope and accuracy of electronic structure techniques. Thus Chapter 8 reviews the current methodologies employed in electronic structure studies of solids with special reference to the qualitative insight which they give into understanding bonding in solids and the quantitative information on charge and spin densities.

Modelling techniques are applicable to a broad range of solids. The present book focuses on non-metallic inorganic systems; detailed discussions of modelling metals can be found elsewhere (e.g. Vitek and Srolovitz, 1989). Particular attention will be paid to oxide, silicate and related systems which include many of the most intensively investigated and important of the inorganic materials. However, the description in Chapter 11 of recent studies of molecular crystals allows us to place the modelling of inorganic materials into a broader context.

Our discussions now continue with an account of the basic aspects of modelling methodologies, which we follow with illustrative examples of recent applications.

2 TYPES OF METHODOLOGY

There are two broad classes of method used in current computational chemistry and physics. The first we will denote as ‘force field methods’. In this approach, knowledge of electronic structures is subsumed into effective interatomic potentials (V), which describe in analytical or numerical form the variation in the energy of the molecule or solid as a function of the nuclear coordinates (r1…rN) of the N atoms present in the molecule or solid. The total potential is generally broken down into ‘pair’, ‘three-body’, ‘four-body’ and higher order terms:

   (1)

(and as discussed in Chapter 7, an initial term v(0) may be included; the primes indicate that in the summations a given term is only included once). V is often approximated by the leading, pair potential term v(2) which depends simply on the distance between the nuclei i and j; and indeed for systems such as ionic crystals in which interactions between the atoms are non-directional, this is generally a good approximation. It is less acceptable for covalent solids in which there is normally strong directionality to the bonding. The pair potential term itself is usually decomposed into Coulombic and non-Coulombic terms (ϕ):

   (2)

where the qi and qj are the effective charges of the atoms. A number of standard analytical functions are available for ϕ, e.g. the Buckingham and Lennard–Jones forms, discussed in Chapter 3 and 11, which are more appropriate for non-bonded interactions. However, as noted, numerical functions may also be used. The types of three-body and higher order terms used in currently available force fields are considered in detail in Chapter 3, while the crucial question of the methods used in summations of the Coulomb interactions is reviewed in Chapter 4.

One of the major thrusts in current computational studies of molecules and solids is the development of high quality force fields. To develop force fields we may use ‘empirical fitting’ procedures in which parameters in the analytical function describing the potential are adjusted via a least squares fitting procedure in order to reproduce as accurately as possible the observed properties of a molecule or crystal. The range of properties must include the structure, while information on vibrational, elastic and dielectric properties is also of great value as discussed in Chapter 3. The second strategy, which has been used for many years, but which is being increasingly refined is to calculate the potentials directly using quantum mechanical methods of the type discussed later. Thus the energy of a molecule or of a pair or cluster of non-bonded atoms is calculated for a variety of geometries and the resulting energy variation is again fitted to an interatomic potential function. The method may also be applied to periodic structures (Gale et al., 1992). Further discussion will follow in Chapter 3.

Having developed a suitable interatomic potential, there is a range of computational techniques which may be employed for calculating structural properties and the dynamical behaviour of molecules and solids, the computational basis of which is now described; subsequent chapters will give more details of the techniques.

3 ENERGY MINIMIZATION

In this simplest of approaches we determine the minimum energy configuration of the molecule or crystal corresponding to the specified interatomic potential. These methods require the specification of an initial configuration or ‘starting point’; the system is then driven (by an iterative procedure) down in energy to the nearest minimum. A wide variety of algorithms are available, which are classified according to the order of the derivative of the total energy function that is employed in the calculation. In general, methods employing second derivatives of the energy with respect to atomic positions are more rapidly convergent than first derivative techniques; and the latter are considerably more efficient than ‘zero derivative’ or search procedures.

Modern minimization methods can be applied effectively and rapidly to large complex systems and, as we will see, are making an increasingly important contribution to real crystallographic problems. The approach is, however, limited for several reasons, of which the following three are the most important:

1. The need for a starting point. This is inherent to this method which, as noted, locates the nearest minimum to the initially specified structure. The first or ‘trial’ structure may be devised by chemical intuition or analogy; approximate experimental information may also be used. There are also a number of more automated procedures. Simulated annealing methods (which employ Monte Carlo algorithms as discussed below) allow very approximate, including random, configurations to be refined to generate a range of candidates for starting points. These methods necessarily employ a cost function which is normally simpler to evaluate than the energy of the system and which measures the quality of the structure. The method allows configurational space to be explored, but in a way that biases the search systematically towards structures with low cost functions. An alternative approach based on genetic algorithms uses evolutionary programming techniques to ‘breed’ successive structures whose probability of survival is dependent on the value of the cost function. Again, random or near random initial configurations can be used to generate plausible starting points. We return to the simulation annealing method below in the context of the Monte Carlo simulation method and Chapter 5 will discuss these techniques and the question of the choice of cost functions in greater detail; an example of the successful use of the genetic algorithm approach will be given later in this chapter.

2. The local minimum problem. This is intimately related to the issue just discussed. Minimization methods find, of course, the nearest minimum to the starting point. All but the simplest molecules and materials have multiple minima and there is no guarantee that the lowest energy structure has been located; indeed as the complexity of the system increases, this becomes an increasingly remote eventuality. The only real solution to the problem is to sample large numbers of starting points in order to ensure that all low energy minima have been identified. The procedures outlined in the previous paragraph are often used in selecting a range of plausible starting points; a number of sophisticated mathematical procedures have been developed with the aim of simplifying the overall potential energy surface and ‘washing out’ local minima (e.g. Kostrowicki and Sheraga, 1992), but there can never be a guarantee that the ‘global’ minimum—the minimum of lowest energy—has been identified.

3. Omission of dynamics. Minimization identifies the static configuration of lowest energy and there is no representation of the vibrational or other dynamical properties of the system. In formal terms, these are ‘zero Kelvin’ calculations, with zero point motion omitted. It is, however, relatively straightforward to add a treatment of the vibrational properties of the system within the harmonic (or quasi-harmonic) approximations. Such methods will be discussed in Chapter 3.

Despite these limitations, minimization techniques are straightforward, robust and readily applicable, and can be applied to systems with large and complex unit cells. They are being used increasingly to refine approximate crystal structures and to calculate the relative energies of different polymorphs, as discussed later in this chapter and in Chapter 3 and 5. Highly complex structures may, moreover, now be modelled routinely as will be apparent in the discussion of silicates in Chapter 9 and high temperature superconductors in Chapter 10.

4 MOLECULAR DYNAMICS (MD)

The basis of these very widely used techniques is again conceptually simple. We simulate the system studied by an ensemble of particles (usually representing atoms, but occasionally groups of atoms) which are contained in a simulation box. Periodic boundary conditions (pbcs) are commonly applied, i.e. the basic simulation box is replicated infinitely in three directions (although 2-D pbcs may be used in surface simulations); in simulations of crystals, the simulation box will comprise the unit cell or, more commonly, a supercell. As the simulations are ‘dynamical’, the atoms are given velocities that are chosen with a target temperature in mind. The simulation proceeds by solving the classical (Newtonian) equations of motion in an iterative manner, in which each iteration (xi) and velocity (vi) of the particles in the simulation box are updated after the lapse of a ‘time step’, Δt, for an infinitesimal value of which we would have the simple update expressions:

   (3a)

   (3b)

where mi and fi are respectively the mass and the total force acting upon the ith particle; the forces are, of course, calculated from the derivatives of the interatomic potentials. Since, in practice, a finite value of Δt must be used, all update algorithms in effect include terms with higher order powers of Δt. The choice of Δt is of critical importance in MD simulations. It must be smaller than the time scale of any important dynamical processes at the atomic or molecular level; thus it must be at least an order of magnitude smaller than the typical period of atomic vibrations (10−12−10−13 s); and the shorter the time step, the more accurate is the numerical integration of the equations of motion. But of course short time steps mean more computational effort for the same amount of ‘real time’ simulation. Values in the range 10−14−10−15 s normally represent the best compromise as discussed in detail by Allen and Tildesley (1987) and by Jacobs and Rycerz in Chapter 4 of this book. These references also review the range of update algorithms used in contemporary MD studies and describe the more sophisticated variants of the technique.

MD simulations therefore proceed by successive applications of the time step, which allows us to develop a dynamical record of the time evolution of the system over the period of simulation. During the early stages of the simulation, the system ‘equilibrates’, i.e. it achieves equipartition of energy and a Maxwellian distribution of velocities. Once equilibrium is achieved, a production run follows, from the analysis of which details of the structure and dynamics of the system may be calculated. Modern simulations involve typically several thousand particles, sampling l00 ps to 1 ns of ‘real time’ (i.e. 10⁵−10⁶ time steps).

MD methods give the most detailed and rich information of any atomistic simulation method. In particular, they have the major advantage of incorporating dynamical (including anharmonic) effects explicitly. They are, however, computationally far more intensive than energy (and free energy) minimization methods. Moreover, the amount of ‘real time’ sampled is limited to the order of nanoseconds even with the largest, most powerful contemporary computers. Dynamical processes with longer time scales cannot therefore be sampled. The real strength of the method in the context of the present book is seen first in the simulation of solids containing mobile atoms or ions, notably the so-called superionic or fast-ion conductors discussed later in this chapter and in Chapter 4: the same chapter will also describe the successes in modelling certain classes of phase transition; while in Chapter 12, Vessal discusses the important application to the generation of models for vitreous materials by directly simulating the melt–quench procedure used in the preparation of glasses.

 kT. An alternative strategy for exploring different regions of the energy surface is the simulated annealing strategy, referred to above, which is based on the Monte Carlo methodologies discussed in the next section.

5 MONTE CARLO TECHNIQUES

Monte Carlo (MC) resembles MD in that successive configurations of the simulated system are generated, but there is no relationship in time between such configurations. Indeed successive configurations are generated by random ‘moves’ which can be an atomic translation or molecular rotation, or the insertion or deletion of an atom or molecule. In this way, ensembles of configurations are accumulated, from which statistical averages may be calculated. In generating such ensembles, it is essential to formulate an ‘acceptance’ criterion, i.e. a procedure that determines whether a new configuration created by a move will be accepted within the ensemble. The most commonly used approach is the Metropolis method, which proceeds as follows:

1. The energy change, ΔE, associated with the move is calculated; from this the Boltzmann factor B = exp (–ΔE/kT) is calculated if ΔE is positive. We note that MC simulations are most commonly run in the NVT (or canonical) ensemble in which both volume and temperature are fixed.

2. If AE is negative, the configuration is accepted and we proceed with another random move. If not, we continue with the next stage.

3. A random number (P) in the range 0–1 is generated.

4. If P < B, the move is accepted; if not, it is rejected. In either case, we continue with the generation of a new move.

The effect of this procedure is to generate an ensemble of configuration that is consistent with Boltzmann statistics.

Like MD, Monte Carlo simulations are typically performed on ensembles containing several thousand particles, to which periodic boundary conditions are applied in the case of the simulation of solids. The simulation again starts with an equilibration phase during which the system is ‘thermalized’, followed by a ‘production run’ in which, typically, several million configurations are generated. We refer once more to the monograph of Allen and Tildesley (1987) for more details of the methodologies employed.

In modelling crystalline solids, the MC technique is of particular value in three distinct fields. The first concerns studies of sorbed systems, e.g. microporous solids loaded with organic molecules. MC techniques are particularly suitable for studying the variation with temperature of the distribution of sorbed molecules in such systems (Yashonath et al., 1988). Secondly, the method has been fruitfully applied to the study of atomic diffusion. In this case the ‘moves’ are atomic jumps of defined frequencies. In complex solids (including, e.g., alloys and ionic conductors), use of the MC technique allows accurate sampling of all the different jump mechanisms contributing to the diffusion, as shown in several studies of Murch and coworkers (e.g. Murch, 1982).

The third class of applications referred to above uses the MC method to explore complex energy surfaces and to find low energy regions, from which minima can subsequently be located by standard minimization procedures. As noted earlier and as discussed in greater detail in Chapter 5, simulated annealing methods have been used with great effect in generating crystal structures from initial random configurations of atoms or ions. We note that the ‘energy term’ in simulating annealing calculations may take a variety of forms. It is commonly, as noted earlier, a simple cost function based on coordination numbers and connectivity. Lattice energies, calculated from Born model potentials may, of course, be employed, but this procedure becomes computationally expensive. It should, however, be noted that simulated annealing procedures employing energies calculated by electronic structure techniques are becoming feasible, although in practice it would seem to be more computationally efficient to use simpler procedures to calculate the energy (or cost function), and to refine the approximate configuration generated by simulated annealing by electronic structure methods when the use of such methods is needed.

The ‘temperature’ used in a simulated annealing study is normally a parameter with no real physical significance. Higher temperatures will result in the acceptance of an increasing number of high energy configurations, allowing the exploration of a wider range of the energy surface but, of course, at increased computational cost. In practice, the simulation usually starts with a high temperature which is then reduced as the lower energy regions of the surface are identified, as further discussed in Chapter 5. Simulated annealing, like MC methods, may also be adapted to the analysis of experimental data. In this case the ‘energy term’ becomes the deviation between calculated data (e.g. the calculated X-ray intensity versus scattering angle for a structural model) and experiment. Such techniques are described as ‘Reverse Monte Carlo’ (RMC) and will be considered in detail in Chapter 6.

The account given above of the basic simulation methodologies will, of course, be extended in subsequent chapters. Further details and discussion may be found in Allen and Tildesley (1987), Catlow et al. (1989) and Catlow (1992). The remainder of this chapter aims to give an impression of the range and scope of simulation studies of inorganic materials by highlighting a number of recent applications.

6 CASE STUDIES

The applications we now discuss relate to the modelling and prediction of crystal structures, to the development of atomistic models for amorphous materials, to the modelling of surfaces of inorganic solids, to the simulation of the dynamical and defect properties of solids and to the explicit calculation of the electronic structure of crystals. They will foreshadow the much more detailed accounts that follow in later chapters.

6.1 Modelling and prediction of crystal structures

Since the 1970s, minimization techniques have been used to model crystal structures, and early work on both molecular and ionic crystals concentrated on reproducing observed crystal structures using suitable interatomic potentials (see Catlow et al., 1993, for a review). Some of the greatest challenges here have been posed by microporous crystal structures, typical examples of which are shown in Fig. 1.1. These materials are attracting growing attention owing to their importance in catalysis, gas separation and ion exchange (see Thomas, 1992) as well as to the fundamental fascination of their crystal architectures. Moreover, their chemical range and diversity continues to expand: to the original aluminosilicate zeolites (constructed from SiO4 and AlO4 tetrahedra linked by corner sharing) were added microporous aluminophosphates (ALPOs) in the early 1980s (Wilson et al., 1982); and substitution of framework tetrahedral (T) atoms by B, Ga, Ge and a wide range of transition metals has become widespread in both zeolites and ALPOs.

Figure 1.1 Microporous (zeolitic) crystal structures showing the sodalite cage (bottom), zeolite A structure (top), sodalite structure (left), and zeolite Y (right).

The work of Sanders et al. (1984), Jackson and Catlow (l988) and Tomlinson et al. (1990) showed that with Born model potentials it is possible accurately to reproduce the crystal structures of silicates including zeolites. A typical example is shown in Plate I which illustrates the calculated and experimental structures of a purely siliceous (i.e. pure SiO2 polymorph) zeolite, silicalite. (A closely related, isostructural material, ZSM-5, which contains a low concentration of Al is an effective isomerization and hydrocarbon synthesis catalyst.) The agreement between theory and experiment is evidently good; more discussion follows in Chapter 9.

More recently, increased use has been made of minimization techniques in refining approximately known structures, which is of particular value in the study of microporous systems as these materials are commonly only available as powders and unassisted refinement by the widely used Rietveld techniques of the powder data for structures of this complexity may be difficult. Several examples illustrate the value of such calculations, as discussed in greater detail in Chapter 9. The first relates to a zeolite, Nu87, synthesized in the late 1980s at the ICI Laboratories in Wilton, UK. The material has useful catalytic properties. Its structure, however, could not be solved, even from high resolution X-ray powder diffraction data collected using Synchrotron Radiation. An approximate structural model was proposed, which was, however, unable to account for all the Bragg peaks in the diffraction pattern of the material, as shown in Fig. 1.2. This model was then used as the starting point of an energy minimization calculation; the resulting minimum, which was of lower symmetry than the initial structure, is shown in Fig. 1.3. This lower symmetry, minimized structure now fully accounts for all the reflections in the diffraction pattern; and indeed, when input into a Rietveld refinement of the powder diffraction data, rapidly yields a low R factor. With the assistance of the energy minimization calculation, the structure has been solved (Shannon et al., 1991).

Figure 1.2 Part of the diffraction pattern for Nu 87. Upper diagram shows experimental data; peaks unassigned on the basis of the model prior to energy minimization are highlighted. Lower diagram is calculated pattern for energy minimized structure. Reproduced by kind permission of Dr P. Cox.

Figure 1.3 Energy minimized structure for Nu 87. Reproduced by kind permission of Dr P. Cox.

Several other examples in the recent crystallographic literature of microporous materials illustrate the power of this combination of powder diffraction and energy minimization techniques. For example, the structures of two recently synthesized aluminophosphates—MAPO36 and DAF1—(Wright et al., 1992, 1993) have been investigated by both powder diffraction and computational methods. The complex structure of the latter, with its two separate and non-communicating channel structures, is shown in Fig. 1.4. Futher examples of the modelling of these systems will be given in Chapter 9.

Figure 1.4 Crystal structure of DAF 1, solved from high resolution powder diffraction data and energy minimization.

As discussed earlier, the greatest challenge in this field is now the prediction of crystal structures, an exercise in global optimization which as we have noted becomes, in practice, a question of identifying a suitable range of ‘starting points’ for subsequent energy minimization. Chapter 5 will describe in greater detail how the challenge of generating plausible initial structures from random starting points is met by the use of the simulated annealing and genetic algorithm procedures referred to earlier. The power of this approach can be illustrated by one example: the recent study of Bush et al. (1995) who solved the structure of a complex ternary oxide, Li3RuO4, which had previously eluded structure determination. Their approach was based on a combination of genetic algorithm techniques (using a simple cost function of the type discussed by Brown in Chapter 2) and energy minimization techniques. The resulting structure (which leads to an acceptable Rietveld refinement of powder X-ray data) is illustrated in Plate II. As will be discussed in greater detail in Chapter 5, there is now a growing number of cases where unknown structures of this order of complexity have been solved by computer modelling techniques.

6.2 Structures of amorphous solids

There is an even greater incentive for the development of reliable computational procedures for modelling the atomistic structures of amorphous solids than for the case of crystalline systems. The development of such models from experimental data is difficult, as the interpretation of Radial Distribution Functions (RDFs) obtained from diffraction data is often ambiguous beyond the first few shells of neighbours. Local structural information produced by Nuclear Magnetic Resonance (NMR) and Extended X-ray Absorption Fine Structure (EXAFS) is of great value,