(Professor Robert A. Evarestov, Professor Vyaches

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R. A. Evarestov V. P. Smirnov
Site Symmetry
in Crystals
Theory and Applications
Second Edition
With 42 Figures
Springer
Professor Robert A. Evarestov
Department of Chemistry, St. Petersburg University
St. Peterhoff, Universitetiskii pr. 2, 198904 St. Petersburg, Russia
Professor Vyacheslav P. Smirnov

Department of Theoretical Physics, Institute of Fine Mechanics and Optics
Sablinskaya 14, 197101 St. Petersburg, Russia
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Max-Planck-Institut fUr Festkorperforschung, Heisenbergstrasse I, 0-70569 Stuttgart, Germany
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Library of Congress Cataloging-in-Publication Data.

Evarestov, R. A. (Robert Aleksandrovich). Site symmetry in crystals: theory and applications 1 R. A. Evarestov,
V. P. Smirnov. - 2nd ed. p. cm. - (Springer series in solidstate sciences, ISSN 0171-1873; \08). Includes
bibliographical references and index. TSBN-13: 978-3-540-61466-1 (softcover: alk. paper). I. Solid state physics. 2. Solid
state chemistry. 3. Crystallography, Mathematical. 4. Symmetry (Physics). I. Smirnov, V. P. (Viacheslav
Pavlovich) II. Title. III. Series. QC176.E8 1997 530.4' II-dc20 96-36380
ISSN 0171-1873
TSBN-13: 978-3-540-61466-1 e-TSBN-13: 978-3-642-60488-1
DOl: 10.1007/978-3-642-60488-1
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Preface to the Second Edition
The first edition of our monograph appeared in 1993 and has already sold out.
As authors we are greatly satisfied that our book appeared to be interesting
for solid-state scientists in different countries. For us it was a great pleasure
to know that a second edition of our book was planned by Springer-Verlag.
In preparing this new edition we took into account the following points.
During these years there was growing interest in the physical and chemical
properties of recently discovered en modifications of carbon (n 2: 60) called
fullerenes. Therefore we have added information about the symmetry groups
of fullerenes C60 and C70 (Sect. 3.2.1), their irreducible (Sect. 3.7) and in-
duced (Sect. 4.1) representations. The space group symmetry of fullerites
(crystals consisting of fullerenes) with rotating molecules is treated in a new
section (Sect. 10.3).
Recent publications on the theory of point defects in crystals use the
super-cell model of an imperfect crystal, which is based on the periodical
repeating of the defect in enlarged unit cells of the host crystal. Therefore we
added (Sect. 6.1.4) information about the symmetry of the super-cell model of
an imperfect crystal.
Section 8.5 contains some new results concerning the phonon properties
of perovskite-like superconductors. The list of references and the subject index
have been enlarged, and misprints and some errors have been corrected.
We are very indebted to Dr. H.K. V. Lotsch of Springer-Verlag for
cooperation in the preparation of this edition.
St. Petersburg, July 1996 R. A. Evarestov

V. P. Smirnov
Preface to the First Edition
The history of applications of space group theory to solid state physics goes
back more than five decades. The periodicity of the lattice and the definition
of a k-space were the corner-stones of this application. Prof. Volker Heine in
Vol. 35 of Solid State Physics (1980) noted that, even in perfect crystals, where
k-space methods are appropriate, the local properties (such as the charge densi-
ty, bond order, etc.) are defined by the local environment of one atom. Natural-
ly, "k-space methods" are not appropriate for crystals with point defects, sur-
faces and interfaces, or for amorphous materials. In such cases the real-space
approach favored by chemists to describe molecules has turned out to be very
useful.
To span the gulf between the k-space and real space methods it is helpful
to recall that atoms in crystalline solids possess a site symmetry defined by the
symmetry of the local environment of the atom occupying the site. The site
symmetry concept is familiar to crystallographers and commonly used by them
in the description of crystalline structures. However, in the application of
group theory to solid state physics problems, the site symmetry approach has
been used only for the last ten to fifteen years. In our book Methods of Group
Theory in the Quantum Chemistry of Solids published in Russian in 1987 by
Leningrad University Press we gave the first results of this application to the
theory of electronic structure of crystals.
In addition to the material of the Russian text, the present book takes into
consideration the newly developed applications of the site symmetry approach
such as the symmetry analysis in lattice dynamics, theory of second order
phase transitions, and magnetically ordered and non-rigid crystals. Chapter 8
was written by Dr. Yu. Kitaev in collaboration with Dr. B. Bairamov and Dr.
M. Limonov.
This text is intended mainly for researchers working in the physics and
chemistry of solids. The authors assume that the reader has attended basic
courses on group theory. This book should also be useful for those primarily
interested in the applications of the site symmetry in crystals: these readers
may start from Chap. 4, entitled "Site Symmetry and Induced Representations
of Symmetry Groups", paying special attention to Sect. 4.5.1. In this section
we explain how to use the tables of simple induced representations of space
groups. Illustrative examples are given in Chaps. 5 - 9.
More than thirty years ago both of us heard lectures by Prof. Mariya I.
Petrashen on group-theory applications in quantum mechanics. For many
years she encouraged our work in this field. Thus we dedicate this book to our
teacher and friend, Professor Petrashen.
VIII Preface to the First Edition
It is a great pleasure to have this opportunity to thank Professor M. Car-

dona not only for the idea to write this book but also for good advice and
hospitality during the visit of one of the authors (R. A. E.) to the Max-
Planck-Institut fUr Festkorperforschung in Stuttgart.
We are especially indebted to Dr. H. K. V. Lotsch of Springer-Verlag for en-
couragement and cooperation. We are very grateful to Dr. A. I. Panin and Dr.
V. A. Veryazov for help in preparing the manuscript and the subject index and
also for help in proofreading.
St. Petersburg, November 1992 R. A. Evarestov

V. P. Smirnov
Contents
1. Introduction .............................................. .
2. Finite Groups and Their Representations ...................... 5

2.1 Elements of Group Theory ............................... 5
2.1.1 Groups. Generators and Generating Relations.
Subgroups. Cosets. Invariant Subgroups.
The Factor Group .................................. 5
2.1.2 Conjugate Elements and Classes. Factorization
of Groups. . .. . . . . .. . . . .. . . . ... . . . .. . . . . .. . . .. . . . .. 7
2.1.3 Homomorphism and Isomorphism of Groups ......... 9
2.2 Elements of Group Representation Theory ................. 10
2.2.1 Representations of a Group. Equivalent, Reducible
and Irreducible Representations. Orthogonality Relations.
Representation Characters ........................... 10
2.2.2 Decomposition of Representations.
Complex Conjugate Representations .................. 15
2.3 Generation of Representations ............................ 17
2.3.1 Direct Product of Representations .................... 17
2.3.2 Subduction of Representations ....................... 20
2.3.3 Induction of Representations ........................ 22
2.3.4 Little Group Method
of Irreducible Representation Generation .............. 26
3. Symmetry Groups and Their Representations .................. 31

3.1 The Euclidean Group and Its Subgroups ................... 31
3.1.1 Translation Group .................................. , 31
3.1.2 Rotation Group .................................... ' 32
3.1.3 Inversion Group ................................... 35
3.1.4 Full Orthogonal Group ............................. 35
3.1.5 Euclidean Group ................................... 36
3.2 Point Symmetry Groups ................................. 39
3.2.1 Symmetry Elements of Molecules
and Crystallographic Point Groups ................... 39
3.2.2 Site Symmetry Subgroups of Point Groups ............ 40
3.3 Space Groups .......................................... 43
3.3.1 Symmetry of a Model of an Infinite Crystal.
Symmorphic and Nonsymmorphic Space Groups ....... 43
X Contents
3.3.2 Symmetry of a Cyclic Model of a Crystal ............. 46

3.4 Site Symmetry in Space Groups ........................... 48
3.4.1 Crystallographic Orbits. Wyckoff Positions ............ 48
3.4.2 Oriented Site Symmetry Groups. Choice of Origin ..... 51
3.4.3 Crystal Structure Types. Crystals with Space Group Dlh. 54
3.5 Symmetry Operations in Quantum Mechanics .............. 55
3.5.1 Symmetry Group of a Quantum Mechanical System. . . . 55
3.5.2 Wigner's Theorem ................................. 56
3.5.3 Time-Reversal Symmetry ............................ 57
3.6 Irreducible Representations of Rotation
and Full Orthogonal Groups ............................. 59
3.7 Representations of Point Groups .......................... 62
3.8 Representations of Space Groups .......................... 70
3.8.1 Irreducible Representations of the Translation Group.
The Brillouin Zone ................................. 70
3.8.2 Stars of Wave Vectors. Little Group.
Full Representations of Space Groups ................ 76
3.8.3 Small Representations of a Little Group.
Projective Representations of Point Groups ............ 78
3.8.4 Double-Valued Representations of Space Groups ....... 79
3.8.5 Dependence of the Labeling of the Irreducible
Representations of a Space Group on the Setting ...... 81
3.8.6 Example: Irreducible Representations
of Space Group D lh. Compatibility Tables ........... 84
4. Site Symmetry and Induced Representations of Symmetry Groups 89

4.1 Induced Representations of Point Groups.
Correlation Tables ....................................... 89
4.2 Induced Representations of Space Groups .................. 91
4.2.1 Induction from Site Symmetry Subgroups
of Space Groups ................................... 92
4.2.2 Induced Representations in the k- Basis.
Band Representations ............................... 93
4.2.3 Simple and Composite Induced Representations ........ 97
4.3 Double-Valued Induced Representations .................... 99
4.4 Generation of the Simple Induced Representations
of the Space Group D lh ................................. 100
4.5 The Twenty-Four Most Common Space Groups: Crystal
Structures and Tables of Simple Induced Representations. . . .. 103
4.5.1 Tables of Simple Induced Representations and Their Use 103
4.5.2 Space Groups and Crystal Structures
with Cubic Lattices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
with Hexagonal and Trigonal Lattices . . . . . . . . . . . . . . . .. 111
with Tetragonal Lattices ............................. 114
Contents XI

with Orthorhombic Lattices ......................... 117
4.5.6 Space Group Setting and Simple Induced Representations
for Monoclinic Space Groups ........................ 121
5. Application of Induced Representations in the Electron Theory

of Molecules and Crystals ................................... 125
5.1 Adiabatic and One-Electron Approximations ............... 125
5.1.1 Space Symmetry
of the One-Electron Approximation Hamiltonian ...... 129
5.2 Induced Representations in the Electron Theory of Molecules 131
5.2.1 Canonical, Localized and Hybridized Molecular Orbitals 131
5.2.2 Localized Two-Center Bonds and Hybridized Orbitals
in AB4 and AB3 Molecules .......................... 136
5.2.3 Multicentered Bonds in the 1,6-C2B4H 6 Molecule . . . . . . . 139
5.2.4 Canonical and Localized Orbitals
in the MnO';- Molecular Ion. . . . . . . . . . . . . . . . . . . . . . . . . 140
5.2.5 Localized Orbitals in the Tetrahedral Bi4 Molecule ..... 142
5.3 One-Electron Approximation for Crystals .................. 144
5.3.1 Crystalline Orbitals.
Degenerate and Nondegenerate Energy Bands. . . . . . . . .. 144
5.3.2 Equivalent Hamiltonians
for the Same Crystal Structures ...................... 146
5.3.3 k-p Perturbation Method in the Energy Band Theory.. 147
5.3.4 Zero-Slope Points of Energy Bands. . . . . . . . . . . . . . . . . .. 150
5.3.5 Energy Bands in the Neighborhood
of Degeneracy Points ............................... 152
5.3.6 Additional Degeneracy of Energy Bands Due
to the Reality of the Hamiltonian .................... 155
5.3.7 Density of States of an Energy Band ................. 155
5.4 Induced Representations and the Theory of Chemical Bonding
in Crystals ...................................... :...... 158
5.4.1 Energy Band States and Localized Functions .......... 158
5.4.2 Localized Orbitals and Atomic States in Crystals ....... 159
5.4.3 Hybridized Orbitals in Crystals ...................... 160
5.4.4 Crystals with Space Group Oh ...................... 161
5.4.5 Crystals with Space Group O~ ...................... 162
5.4.6 Crystals with Space Group Dlh ...................... 163
5.4.7 One-Electron States in High-Tc Superconductors ....... 165
5.5 Energy Bands and Localized States ........................ 173
5.5.1 Localized Orbitals and Parameters of an Energy Band .. 173
5.5.2 Generation of Localized Functions in Crystals ......... 174
5.5.3 Interpolation Scheme Using Localized Functions ....... 175
5.6 Localized Orbitals in Molecular Models of Crystals ......... 179
5.6.1 Cluster Model of Perfect Crystals .................... 179
5.6.2 Cluster and Crystal Localized Orbitals ................ 180
XII Contents
5.6.3 Energy Bands of AgBr from Cluster Calculations

of [Ag 14Br 131 + ................................. 181
5.6.4 Cyclic Model as a Molecular Model of Crystals. . . . . . . . 182
5.6.5 Localized Orbitals in the Cyclic Model ... . . . . . . . . . . . .. 183
6. Induced Representations in the Theory of Imperfect Crystals .... 185

6.1 Point Defects in Crystals ................................. 185
6.1.1 Single Defect Model ................................ 186
6.1.2 Cluster Model of Imperfect Crystals .................. 188
6.1.3 Cyclic Model of Imperfect Crystals ................... 189
6.1.4 Band Model of Imperfect Crystals ................... 189
6.1.5 Localized Orbitals in the Band Model of Point Defects. 191
6.2 Diperiodic Space Groups. Surface Electron States ........... 192
6.2.1 Diperiodic (Layer) Space Groups ..................... 192
6.2.2 Site Symmetry in Layer Groups ...................... 195
6.2.3 Irreducible Representations of Diperiodic Groups ...... 197
6.2.4 Induced Representations of Diperiodic Groups ......... 199
6.2.5 Use of Translational Symmetry in the Comparison
of Bulk and Surface Crystalline States ................ 201
7. Application of Induced Representations of Space Groups

to Second Order Phase Transitions ........................... 205
7.1 Symmetry Rules in the Landau Theory
of Second Order Phase Transitions ........................ 205
7.2 Tensor Fields in Crystals and Induced Representations
of Space Groups. Tensor Fields for Space Group D lh ........ 207
7.3 Vibrational Field Representation and Phase Transitions
in High-Temperature Superconductors ...................... 210
8. Induced Representations of Space Groups

in Phonon Spectroscopy of Crystals .......................... 213
8.1 Phonon Symmetry Analysis .............................. 213
8.2 Infrared and Raman Spectra Selection Rules ................ 214
8.3 Phonon Symmetry and Optical Spectra Selection Rules
in Semiconductor Superlattices ........................... 215
8.3.1 (GaAs)m(AlAs)n Superlattices ....................... 216
8.3.2 (Si)m(Ge)n Superlattices ............................. 221
8.3.3 Experimental Applications .......................... 221
8.4 Phonon Symmetry in High-Temperature Superconductors ..... 227
8.5 Phonon Symmetry in Diperiodic Systems .................. 233
9. Site Symmetry in Magnetic Crystals

and Induced Corepresentations ............................... 237
9.1 Shubnikov Space Groups of Symmetry of Magnetic Crystals . 237
9.2 Site Symmetry in Magnetic Crystals ....................... 238
9.3 Corepresentations of Shubnikov Space Groups .............. 241
Contents XIII
9.4 Induced Corepresentations of Magnetic Space Groups ..... 244

9.5 Corepresentations of the Space Groups
of Antiferromagnetic La2Cu04 .......................... 247
10. Site Symmetry in Permutation - Inversion Symmetry Groups

of Nonrigid Crystals ....................................... 251
10.1 Symmetry Groups of Nonrigid Crystals .................. 252
10.1.1 Labeling of Nuclei. Sampling of Coordinate Systems 252
10.1.2 Description of Permutation -
Inversion Symmetry Elements .................... 253
10.1.3 Coordinate Transformations Induced
by Permutation - Inversion Symmetry Elements ... 255
10.1.4 Site Symmetry Group of a Rotating Molecule
in a Nonrigid Crystal ............................ 256
10.1.5 Permutation - Inversion Group
of a Nonrigid Sodium Nitrate Crystal ............. 257
10.2 Irreducible Representations
of a Nonrigid Crystal Symmetry Group. . . . . . . . . . . . . . . . .. 260
10.2.1 Generation of Irreducible Representations .......... 260
10.2.2 Irreducible Representations
of a Site Symmetry Group ....................... 261
10.2.3 Classification of States .......................... 263
10.3 Generalized Symmetry of High-Temperature Phase
of Fullerite C60 264
10.3.1 Permutation - Inversion Symmetry Group
of Fullerite C60 in the High-Temperature Phase .... 265
10.3.2 Irreducible Representations
of the Groups [nJ and Pc ........................ 265
10.3.3 Classification of States of Nonrigid Fullerite C60 . 266
References .................................................... 269
Subject Index ................................................. 277

1. Introduction
In the past 15 or 20 years a number of books have been published dealing with
the description of group theory applications in solid-state physics. Both books
treating the foundations of the space group theory and containing the irreduc-
ible representations of these groups [1.1-5] and books giving the reader an
evaluation of the current state of the various possible applications of this theory
[1.6-14] have appeared. It would therefore seem to be appropriate to give some
justification for offering to the reader yet another text on this subject. As far as
we know the present book is the first attempt to systematically arrange all the
group theoretical aspects of the site symmetry approach to crystalline solids and
to consider different applications of this approach.
In applications of the group theory to a crystalline solid the latter is con-
ceived as a physical system which is transformed into itself under space group
symmetry operations. The methods of the space group theory allow classifica-
tion of the delocalized crystalline states (electron, phonon, etc.) with respect to
irreducible representations, and obtaining selection rules for transitions in a
crystal as a whole system. In this traditional approach the symmetry properties
of the environment of constituent atoms are, as a rule, ignored, which results in
a loss of information about the connection between the symmetry properties of
atomic and crystalline states. The present book intends to show that if we use
not only the space symmetry of a crystal as a whole but also the site symmetry
of different groups of atoms in it we can considerably extend the possibilities of
the group theory applications.
The symmetry analysis of the connection between extended and localized
states in a crystal requires information about the site symmetry of an atom in a
crystal, i.e., the knowledge of such a subgroup G, of a full space group G whose
transformations leave invariant the direct lattice point q occupied by an atom.
Establishing the symmetry connection between atomic and crystalline states
means, in terms of group theory, the generation of space group G representa-
tions induced by the representations of its site symmetry subgroup G,.
Chapters 2-4 contain the group-theoretical information necessary for the
applications of the site-symmetry approach to various solid-state physics prob-
lems. In Chap. 2 we briefly consider the finite groups and their representations.
The most important tools in the site-symmetry theory are the induced represen-
tations of finite groups and the little group method, which are considered in
greater detail.
In Chap. 3 we give a descriptive account of the symmetry groups and their
representations. To keep the size of this text manageable we had to restrict
R. A. Evarestov et al., Site Symmetry in Crystals

Springer-Verlag Berlin Heidelberg 1997
2 1. Introduction
ourselves somewhat and refer readers to [1.2,4,6]. Special attention is paid to

the site symmetry in space groups (Sect. 3.4) and the dependence of the notation
of space group irreducible representations on the choice of the setting and ori-
gin, which differs in the various tables available.
Chapter 4 may be considered as the most important in the group-
theoretical foundations of the site-symmetry approach. We discuss in detail
the concepts of band, simple and composite induced representations of space
groups. By considering an example of the space group Dlt we analyze
the procedure of simple induced representation generation. This chapter also
contains tables of simple induced representations for 24 frequently occurring
space groups. In Sect. 4.5.1 we explain a way of using these tables.
In Chaps. 5-10 we consider various applications of the site-symmetry
approach to crystals with Fedorov and Shubnikov space group symmetry.
In the theory of electronic states of crystals extended (Bloch) and localized
(Wannier) functions are used interchangeably. The Bloch states considered in
electron band theory are eigenfunctions of the one-electron equation for an
electron in a periodic potential, so the representation theory of space groups can
be applied to their symmetry classification. The localized crystalline orbitals
(considered in the theory of chemical bonding in crystals and in the theory of
point defects) are not eigenfunctions of this equation, so the ordinary space
group irreducible representation theory is not applicable to them.
In Chap. 5 we discuss the application of induced representations in the
electron theory of molecules and crystals. It is shown that the use of the site-
symmetry approach and simple induced representation tables allows one to
quickly analyze the symmetry of crystalline orbitals in complex crystals, in spite
of there being many atoms in a unit cell, and also to make some qualitative
conclusions about the character of chemical bonding, provided the symmetry
properties of electron states of upper valence bands are known.
As the use of molecular models of crystals appears to be increasingly popu-
lar in solid-state theory, a problem arises of relating electron band states to
molecular orbitals obtained. In Sect. 5.6 we show that transforming band states
to localized (based on site-symmetry analysis) orbitals allows one to use the
results of molecular cluster calculations to discuss the band states of a perfect
crystal.
In Chap. 6 we consider the appplication of induced representations to the
electron theory of imperfect crystals. It is shown that by using site symmetry and
induced representations one obtains symmetry information about the possible
mixing of perfect crystal (band) states with the localized (impurity) state of a
given symmetry.
The problem of establishing the connection, by symmetry, between local-
ized and delocalized one-electron functions arises also in systems having two-
dimensional periodicity in space (surfaces of crystals, slabs as two-dimensional
models of crystals, thin films and so on). The symmetry of these systems is
described by two-periodic (layer) space groups. The theory of the induced repre-
sentations of these groups is discussed in Chap. 6. It is shown that the irreduc-
1. Introduction 3
ible representations of the layer space groups (small and full) are subduced by
the irreducible representations (irreps) of the corresponding three-periodic space
groups. So the tables of simple induced representations oflayer space groups are
contained in the tables of simple induced representations of the corresponding
three-periodic space groups.
In Chap. 7 it is shown that the use of site symmetry significantly facilitates
the symmetry analysis of the second order phase transitions in crystals. A phase
transition, being the result of a change in some physical property of a crystal, is
restricted by the tensor field criterion that the irreducible representation of
space group G driving the phase transition must be contained in a tensor field
representation. The latter is, in fact, the induced representation of a space group.
The use of the site-symmetry approach in lattice dynamics problems (Chap.
8) allows one to make rapid group-theoretical analyses of phonon symmetry not
only at the Brillouin zone center (k = 0) but also in the entire Brillouin zone.
Such an analysis, when made by the usual techniques, is rather cumbersome.
To demonstrate the efficiency of the site-symmetry approach for crystals
with many atoms in the unit cell we have considered the symmetry of crystalline
high-temperature superconductor electron (Chap. 5) and phonon (Chap. 8)
states and phase transitions in La Z Cu0 4 (Chap. 7). Bearing in mind the consid-
erable current theoretical and experimental interest in the study of semiconduc-
tor superlattices we consider in Chap. 8 the phonon symmetry and optical spec-
tra selection rules in semiconductor superlattices (GaAs)m(AIAs)n and (Si)m(Ge)n.
In Chaps. 4-8 we deal with site symmetry and induced representations of
non-magnetic crystals with a symmetry of Fedorov space groups G. The sym-
metry of magnetically ordered crystals is described by Shubnikov space groups
S. These symmetry groups contain the operation ao of a magnetic moment
reversal in addition to all the spatial symmetry operations of G. The operation
ao is anti-unitary so that it is necessary to extend representation theory to
groups which contain anti-unitary operators. This extension brings corepre-
sentations of magnetic point and space groups.
In Chap. 9 we briefly consider site symmetry in magnetic crystals and its use
in the theory of induced corepresentations. Some examples of application of this
theory are also given.
Both non-magnetic and magnetic crystal symmetry groups describe systems
which we consider rigid since the atoms in them take part only in small vibra-
tions around the equilibrium positions of nuclei. The latter define the symmetry
group of a crystal. The symmetry analysis may be extended to non-rigid crystals,
i.e., systems with groups of atoms taking part in some sort of large-amplitude
motion-internal rotation, inversion, larger-amplitude binding, etc. This exten-
sion requires introducing permutation-inversion symmetry groups and their
irreducible representations. The site symmetry in non-rigid crystals is consid-
ered in Chap. 10.
2. Finite Groups and Their Representations
In this chapter we give a brief survey of the basic concepts of abstract groups and their representa-
tions. Most statements in the following sections are given without proof, which, however, the reader
can find elsewhere, e.g. [2.1-3].
2.1 Elements of Group Theory
2.1.1 Groups. Generators and Generating Relations. Subgroups. Cosets.

Invariant Subgroups. The Factor Group
A set G of elements 9 (g E G) is called a group if:
1) A binary algebraic operation is defined on the set G, that is, every pair of
elements taken in a particular order is related to an element of the set,
(2.1.1)
This operation is called the composition law ("group multiplication", or

more simply, "multiplication").
2) The multiplication is associative,
(2.1.2)
3) There exists in the set G an identity (or unit) element E such that
gi E G 1 (2.1.3)
4) Each element 9 of the set G has in the set G an inverse (or reciprocal)
element g-l such that
I g-lg = gg-l = E , g,g-l E G. (2.1.4)
It is easy to show that the identity element in the group is unique and that
the inverse of every element of G is also unique. A group G is finite if the number

6 2. Finite Groups and Their Representations
n of its elements is finite (n is the order of G). Otherwise a group is infinite (if the
number of elements is countable) or continuous. For finite groups the fourth
point of the definition is a consequence of the others. If gigj = gjgi for every
gi' gj E G the group is commutative (or Abelian).
For finite groups the composition law can be given as a multiplication
table, the rows and columns of which correspond to the group elements. The
intersection of the gi-th row and the grth column contains the product gigj =
gk E G.
Every row in the multiplication table contains all the elements of the group
and can be obtained by the multiplication (from the left) ofthe first row elements
by the first element of the row in question. We have the same thing for the
columns. But the multiplication of the first column elements by the first element
of other columns has to be done from the right.
A subgroup H is defined as a subset of G, which is itself a group with the
same composition law: H c G. Any subset of G which is closed with respect to
the multiplication law forms a subgroup as the other requirements of the group
definition are fulfilled automatically.
In the sequence of different powers of an element g of a finite group
(2.1.5)
the members will be regularly repeated. If the repetition begins with the element
gk+l = ggk then gk = E (k is called the order of the element g). The set of
elements
(2.1.6)
is a commutative subgroup of G. Groups of this kind are called cyclic. Since
gk = ggk-l = E then gk-l = g-l and for a finite group the existence of inverse
elements can be omitted in the group definition.
Any element of a finite group can be represented as a finite product of some
elements raised to different powers. They are called generators (or generating
elements). The choice of generators is not unique. To determine a group com-
pletely it is necessary to also give the so-called generating (or defining) rela-
tions which reduce the infinite number of different products of generators to
a finite number of group elements. For example, a cyclic group of order n is
determined by the sole generator g and the sole generating relation gn = E.
Let H be a subgroup of G (H c G) with elements hk (k = 1,2, ... , nH ). A set
giH of nH elements gih (h E H c G and gi E G) is a left coset of the group G with
respect to its subgroup H. The co sets giH and gjH either have no common
elements or coincide. All the cosets have nH different elements. The number of
different cosets is equal to t = nG/nH and is called the index of H in G. The group
G may be regarded as a sum of t = nG/nH left cosets
(2.1.7)
2.1 Elements of Group Theory 7
Elements gi are representatives of the (left) cosets. Any element of a coset may be
taken as its representative. If gi E H then the coset is a subgroup itself. The other
co sets are not subgroups as they have no identity element; they are not closed
with respect to the multiplication law.
The right cosets Hgi may be determined in the same way. In the general
case, a left coset giH does not coincide with a right one Hg i. If there is coinci-
dence then the subgroup H is called invariant (or normal, H <J G), i.e., for an
invariant subgroup H <J G
or for all gi E G . (2.1.8)
In the case of an invariant subgroup H <J G the cosets giH may be regarded
as members of a factor group (or quotient group) of order t = nG/nH with com-
position law
(2.1.9)
The factor group is denoted G/H. In this group the identity element is the
invariant subgroup itself, the inverse element of giH is gi- 1H.
2.1.2 Conjugate Elements and Classes. Factorization of Groups

An element g' qgq-1 is said to be conjugate to 9 by means of q. Since
=
9 = q-1 g'(q-1 rthe element 9 is conjugate to g' by means of q-1. Thus the
1
conjugation relation is reciprocal. This relation is also transitive. Two elements

conjugated to any element of G are conjugate to each other: if gl = qg3q-1 and
g2 = pg3P-1 then gl = (qp-1)g2(qp-1)-1.
A subset S of elements of G which are conjugate to each other forms a class
(conjugacy class). The number of elements in a class is its order. Any class is
determined uniquely by any of its elements.
A set of elements q E G commuting with a fixed element c forms a subgroup
Qc called the normalizer of c in G. In the decomposition of G into left co sets of Qc
(2.1.10)
all the elements of a coset gjQc generate the same element conjugated to c
(2.1.11)
which differs from the elements generated by other cosets. Hence the set of nG
elements gcg- 1 where 9 runs over all the elements of G contains every element
of the class S the same number of times. Thus the class order ns is a divisor of
the group order nG Any element of G is a member of only one class. A group
G may be partitioned into disjoint classes. An element commuting with all
elements of G (self-conjugate element) forms a class. For example, the identity

element of G is always a class of order one. According to (2.1.8) an invariant
subgroup consists of whole classes of the group G.
Let a group G be decomposed into right cosets with respect to its subgroup
H
(2.1.12)
The product gigj of coset elements, which is an element of G, is a member of

some coset
hEH. (2.1.13)
In general, the set of elements gi from (2.1.12) is not a group, as it is not closed
with respect to the composition law of the group G. The element gk is a product
gigj to within an element h E H
(2.1.14)
The element h is labeled with indexes i andj because a given multiplier h E H is

related to every pair of elements gigj. The multiplier h depends also on the
choice of a representative gk of the coset Hg k. The set of elements gi in (2.1.12)
with modified composition law (2.1.14) is said to be a group Q modulo H and is
denoted as QH. Its order nQ is equal to the index of H in G (nQ = nG/nH).
As it follows from (2.1.12), any element of G may be written as a product
(2.1.15)
The group G is called the conditional product of the group H and the group QH
(modulo H)
(2.1.16)
The sets Hand QH have no common elements except the identity element.
It may happen that the elements gi in (2.1.12) themselves form a group Q.
Then the group G is said to be the weak direct product of its two subgroups
(2.1.17)
If H is an invariant subgroup of G (H <J G) then G is called a semidirect

product of Hand Q
(2.1.18)
Finally, if both Hand Q are invariant subgroups of G then G is the direct

2.1 Elements of Group Theory 9
product of Hand Q
(2.1.19)
In the latter case higj = gjh i for all hi E Hand gj E Q. In fact, an element
gjhig j- I hi -I belongs to the group H
(gjhig j -I )h i-I E H , (2.1.20)
as well as to the group Q
g}higj-Ihi-I) E Q, Q<l G . (2.1.21)
Since the identity element E is the only common element of the groups Hand Q
then
and (2.1.22)
A conjugacy class S(G) of the group G = H x Q consists of the elements
(2.1.23)
hihh i-I E S(H) E H ,
i.e., it contains all kinds of products of elements from the classes S(H) and S(Q) of
the groups Hand Q, respectively. The S(G) class order nS{G) is equal to the product
of S(H) and S(G) class orders,
(2.1.24)
The number kG of classes in G is equal to the product of numbers of classes in

H and in Q:
(2.1.25)
2.1.3 Homomorphism and Isomorphism of Groups

A many-to-one correspondence between elements of groups G and G' is a
homomorphism G -+ G' if this correspondence is preserved in the composition
law. In other words, if
g;,gj E G') (2.1.26)
and
(2.1.27)
then there exists a homomorphous mapping of the group G onto G' (G --+ G').
The elements g;, gj E G' are images of the elements gi' gj E G. Under a homomor-
phism G --+ G' a few elements of G have the same image in G'. A subset NeG
of elements in G, which have the identity element E' as their image in G', is called
the kernel of the homomorphism. The kernel N is a normal subgroup in G
(N <J G).
The elements of a coset giN in the decomposition of G with respect to N are
mapped onto the same element g i E G'. Different cosets of G are always mapped
onto different elements of G'. The orders of groups G, G' and N are related by
(2.1.28)
When a kernel N consists of a single element (the identity E) there is a

one-to-one correspondence between the elements of groups G and G' called
group isomorphism
(2.1.29)
Isomorphic groups have the same order.

If G --+ G' is a group homomorphism and N is its kernel then the factor
group GIN is isomorphic with the group G' (GIN - G').
2.2 Elements of Group Representation Theory
2.2.1 Representations of a Group. Equivalent, Reducible

and Irreducible Representations. Orthogonality Relations.
Representation Characters
A representation (rep) of a group G (g E G) is a group GD of linear operators
D(g) = {j in a vector space L which is a homomorphous image of the group G.
The space L is called the space of the rep and its dimension n is the dimen-
sion of the rep. Any basis in L is called the basis of the rep. Since G --+ GD ,
(2.2.1)
If ei (i = 1,2, ... , n) is a basis in the rep space L then the operator D(g) is
defined by the matrix D(g):
D(g)ei = L Dji(g)ej . (2.2.2)

j
An operator D(g) transforms a vector x with components Xi

2.2 Elements of Group Representation Theory 11
x == ~ xie i (2.2.3)
i
in the space L into the vector x' also in the space L
x' == 15(g)x == ~ xi15(g)ei ==

i
L X;Dji(g)ej == L xiej
ij j
(2.2.4)
(2.2.5)
A rep space L is said to be invariant under all the operators of the rep.
The set of matrices D(g) (g E G) itself forms a group with the usual matrix
multiplication as the composition law. Moreover,
(2.2.6)
This group of matrices D(g) is called the matrix rep of the group G.
If 1 is a nonsingular operator and 15(g) is a rep of a group G then the group
of operators
1 15'(g) == 115(g)1-1 1 (2.2.7)
is also a rep of G. This rep is said to be equivalent to the rep 15(g). Equivalency
is a property which is reciprocal and transitive.
In the basis e;(i == 1,2, ... , n) an operator 1 has a matrix A:
lei == L Ajiej
j
(2.2.8)
and the operator (2.2.7) has a matrix

D'(g) == AD(g)A -1 . (2.2.9)
The matrices D'(g) (g E G) also give a matrix rep of G, which is equivalent to the
rep by the matrices D(g).
The relation (2.2.8) can be regarded as a transition to a new basis e; == lei
in the space L. In this interpretation the matrices D(g) and D'(g) correspond
to the same operator 15(g) but in two systems of basis vectors ei and e;
(i == 1,2, ... ,n). Thus the choice of different nonsingular operators 1 in (2.2.7)
[or matrices A in (2.2.9)] generates an infinite number of reps equivalent to the
initial one 15(g) [or D(g)].
A rep consisting of unitary operators (or matrices) is called a unitary rep. It
may be proven that any rep of a finite group is equivalent to a unitary one. This
is true also for some infinite and continuous groups. In this book we restrict
ourselves to unitary reps.
A rep is faithful if the mapping g --+ D(g) is isomorphous. For any group
there exists a trivial one-dimensional rep where every element of G is mapped to
1 (or to the identity operator). This is the identity (or unit) rep.
A rep D(g) is reducible if in the space Ln of this rep there is a subspace Lk of
smaller dimension (k < n) invariant under all the operators D(g) (g E G). Other-
wise a rep D(g) is an irreducible representation (irrep).
The matrices of a reducible rep D(g) in some arbitrary chosen basis em
(m = 1,2, ... , n) have the general form
D(g)em = L Dpm(g)ep . (2.2.10)

p
The space L of a reducible rep can be decomposed into a direct sum of

invariant subspaces Vi), every subspace being a space of some irrep:
t
L = " L(i) (2.2.11)
n L... "j'
i=1
t
Lni=n. (2.2.12)
i
Let e/i) (j = 1,2, ... , nJ be a basis in the space L~: (i = 1,2, ... , t). A set of
vectors e/) forms in the space L a basis of the rep which is related to the initial
one em by a matrix A
(2.2.13)
m
In the latter basis the matrices of the reducible rep have a special, completely
reduced, quasi-diagonal form
(2.2.14)
with the matrices D(i)(g) of irreps in the main diagonal. The rep D(g) is called the
direct sum of irreps D(i)(g). Every irrep may occur several times ri in D(g). The
number ri is the multiplicity of the irrep D(i)(g) in the reducible rep D(g). Usually
the decomposition of a reducible rep into irreps is written as
D(g) = L rp(i)(g) . (2.2.15)

i
This relation means that there exists a matrix A such that matrices of the equiv-
alent rep D'(g) = AD(g)A -1 have the quasi-diagonal structure (2.2.14).
The matrices of irreps have some remarkable properties. They satisfy
Schur's two lemmas.
Schur's first lemma. A single nonzero matrix S commuting with all the
matrices of an irrep of some group G
D(g)S = SD(g) (2.2.16)

is a multiple of the unit matrix
S=kE. (2.2.17)
Schur's second lemma. Let the matrices D(a)(g) and D(P)(g) (g E G) form two
inequivalent matrix irreps of dimension na and np of a group G. Any matrix B
with na rows and np columns satisfying the relation
(2.2.18)
for all g EGis a zero matrix (B = 0).

Both of Schur's lemmas are valid for unitary irreps as well as for non unitary
ones.
A criterion of irreducibility of a rep can be formulated on the basis of
Schur's first lemma: A rep is irreducible if there is no nonzero matrix differing
from a multiple of the unit matrix and commuting with all the rep matrices.
With the help of Schur's lemmas the following orthogonality relations for
the matrix elements of unitary irreps can be proved:
(2.2.19)
The character of an element g E G in a rep D(g) is defined as the trace of the

matrix D(g):
x(g) = Tr{D(g)} = 'LDii(g) . (2.2.20)

i
The character of a rep D(g) [or D(g)] is the set of X(g) for all g E G.
Characters of reps have the following properties:
1) The characters of equivalent reps are equal to each other
x'(g) = Tr{D'(g)} = Tr{AD(g)A- 1} = Tr{D(g)} = X(g) (2.2.21)
2) All the elements of a conjugacy class have the same character:
X(giggi- 1) = Tr{D(gi)D(g)D-1(g;)}
= Tr{D(g)} = X(g) . (2.2.22)
3) The character of a reciprocal element g-l is a complex conjugate to the

character of g:
X(g-l) = Tr{D-l(g)} = Tr{D+(g)}
= Tr {D*(g)} = X*(g) . (2.2.23)
In (2.2.23) the matrix D(g) is assumed to be unitary [D-1(g) = D+(g)]. But

the result is obviously valid also for non unitary reps, as all equivalent reps
have equal characters.
4) The character of the identity element is equal to the rep dimension
X(E) = n . (2.2.24)
5) Taking in (2.2.19) p = q and 1= m and then summing over q and m, we

obtain the orthogonality relations for characters of irreps:
L X(i)(g) [XU)(g)]* = nGDij (2.2.25)

gEG
or otherwise
kG
"~ss D
n X(i)[X sU)]* = nGlJ' (2.2.26)
s
where ns is the order of a class C and the sum is over all the kG classes of a
group G.
6) Let X(g) be the character of a reducible rep and D(g) be the matrices of this
rep in the basis (2.2.13), i.e., have the block structure (2.2.14). It is obvious
that
x(g) = L rili)(g) , (2.2.27)

i
where ri is the multiplicity of the irrep D(i)(g) in a reducible rep D(g). Using
the orthogonality relations (2.2.25) or (2.2.26) we obtain for the multi-
plicities r i
(2.2.28)
7) For a rep D(g) of a group G with the characters X(g) (2.2.27) let us calculate
L [X(g)[2 = L rirj L X(i)(g)[XU)(g)]*

gEG ij gEG
(2.2.29)
The equality holds if among the multiplicities ri only one (rio) is nonzero and
equal to one, i.e., if the rep D(g) is irreducible and equivalent to D(io>(g).
Therefore the relation
(2.2.30)
can be used as the irreducibility criterion of a rep with the character X(g) for
a finite group.
2.2.2 Decomposition of Representations. Complex Conjugate Representations

Let ej be the basis in the space Ln of a reducible rep D(g) of a group G (g E G).
The space Ln may be decomposed into subspaces V ap ) invariant under the
operators D(g) and transforming according to the irreps D(a)(g) of G. The
multiplicities of irreps D(a)(g) in D(g) are given by (2.2.28). A symmetry-adapted
basis in Ln
(i = 1,2, ... ,na, P = 1,2, ... ,ra) (2.2.31)
is generated by the operators
Fija) = (na/nG) L (D&a)(g*D(g) (2.2.32)

geG
Using (2.2.19) we find as a result of action of the operator Fija) on elf)

Pijea) ekp
(p) _ ~ ~ (a)
- UapUjkeip . (2.2.33)
Hence, acting with Fija) on the basis vector ej in Ln
Fija)ej = (na/nG) I [D[j)(g)]*D(g)ej , (2.2.34)

geG
we obtain a vector proportional to e\a) or equal to zero if ej does not contain the
latter. If D(a)(g) appears ra times in D(g) then there are ra linear independent sets
of vectors e\~ (p = 1,2, ... , ra) transforming according to the irrep D(a)(g). They
can be generated as follows.
Among the vectors Ffal ej (j = 1,2, ... , n) there are just ra linearly indepen-
dent first basis vectors of irrep D(a)(g). Using Schmidt's procedure of ortho-
gonalization we obtain ra vectors en (p = 1,2, ... , ra) which have the property
(2.2.35)
The rest of the vectors in the spaces L (ap) are generated via
(i = 2, ... , na, p = 1,2, ... , ra) . (2.2.36)

The vectors el~ form an orthogonal symmetry-adapted basis in Ln:

(2.2.37)
Moreover, the vectors e\:) with fixed Ct. and p form a subspace L(a.p~ invariant
under all the operators 15(g) and transforming according to the irrep D(a.)(g).
The operator
p(a.) = L Pi\a.) = (na./nG) L [X(a.)(g)]*15(g) (2.2.38)

i 9
leaves unchanged any vector in any subspace of Ln transforming according to

the irrep D(a.)(g) and turns all the others into zero:
(2.2.39)
i.e., it is a projection operator onto the subspace of the irrep D(a.)(g). If D(a.)(g) is
contained ra. > 1 times in L then the operator (2.2.38) picks out from L a reduc-
ible subspace
L(a.) = L'. Va.p) . (2.2.40)

p=l
Further decomposition of L(a.) into irreducible subspaces L(a. p) can be done with
the help of the operators (2.2.32).
Let 15(g) [D(g)] be a rep of a group G in complex veclor space Ln and ei
(i = 1,2, ... , n) be complex basis vectors in Ln. An operator D(g) complex conju-
gate to an operator 15(g) is determined by
D(g)e{ = (D(g)eJ* = L DjT(g)ej , (2.2.41)

j
i.e., the matrix D(g) of the operator D(g) in the basis e{ is complex conjugate to
the matrix D(g) of the operator 15(g) in the basis ei:
D(g) = D*(g) . (2.2.42)
A set of operators D(g) (g E G) [and the set of matrices 15(g) = D*(g)] also
forms a rep of the group G. It is called complex conjugate with respect to the rep
15(g) [or to matrix rep D(g)] and has the characters
I X(g) = [X(g)]* . I (2.2.43)
If all characters are real, i.e.
x*(g) = X(g) for all g E G , (2.2.44)

2.3 Generation of Representations 17
the reps D(g) [D(g)] and D(g) [D(g) = D*(g)] are equivalent to each other.
Hence there exists a nonsingular operator A (nonsingular matrix A) such that
D(g) = AD(g)A- 1 , (2.2.45)
I D*(g) = AD(g)A -1 (2.2.46)
A rep equivalent to a rep with real matrices is called real. It may be proved
that for real reps the matrix A in (2.2.46) is symmetric
(2.2.47)
If x*(g) = X(g) for all g E G, but the rep is not real, the matrix A in (2.2.46) is
antisymmetric
(2.2.48)
For a finite group the reality of an irrep can be established with the help
of the following criteria:
if D(g) is a real irrep;

if D(g) is inequivalent to D*(g);
(2.2.49)
if D(g) is equivalent to D*(g), but
is not real.
2.3 Generation of Representations
2.3.1 Direct Product of Representations

Let D(~)(g) and j)(P)(g) be reps of a group G in spaces L(~) and L(P) of dimensions
n~and np respectively.
D(~)(g)el~) = L DI~l<g)el~) , (2.3.1)
i'
D(P)(g)eJP) = L DJPJ(g)eJP) , (2.3.2)

j'
A set of possible pairs
(i = 1,2, ... ,n~,j = 1,2, . .. ,np) (2.3.3)
forms a space L = L(~) x L(P) of dimension n = n~np called the direct product of
spaces L(IZ) and L(P). Define in the space L the operators j)(g) = j)(IZ)(g) x j)(P)(g)
as follows:
(2.3.4)
A matrix D(g) = D(IZ)(g) x D(P)(g) with elements
(2.3.5)
is said to be the direct product of the matrices D(IZ)(g) and D(P)(g). The operators
j)(g) [the matrices D(g)] can be checked to be a rep of G which is called the
direct product of reps j)(IZ)(g) and j)(P)(g) [or matrix reps D(IZ)(g) and D(P)(g)]. Its
characters are
(2.3.6)
A direct product of irreps IX and /3 is, in general, reducible and may be

decomposed into irreps of G
D(IZ)(g) x D(P)(g) = L r}IZP) D(Y)(g) . (2.3.7)

Y
This is the so-called Clebsch-Gordan decomposition. The multiplicities r}IZP)

(Clebsch-Gordan coefficients) are found in the usual way
r}IZP) = nc/ L [iY)(g)]*X(IZ)(g)X(P)(g) . (2.3.8)

9
Let ei~ (k = 1,2, ... , ny, p = 1,2, ... , r}IZP) span in the space L = VIZ) X VP)
the subspaces L(Y) of the irreps D(Y)(g) contained in D = D(IZ) X D(P). The basis
vectors e(Y)
~
are linear combinations of e!lZ)e!P)
, J
e(Y) = "(IX i
kp ~ '"
/3 J'I')' " k p)e!lZ)e!P)
l J
(2.3.9)
ij
The numbers (IX, i, /3,jl')', k, p) are Clebsch-Gordan (or Wigner) coefficients. They
form a unitary matrix if the sets of vectors ei~ and e!lZ) ejP) are orthonormal bases
in L.
The direct product of irreps D(~) x [D(P)]* contains the unit irrep, only
once, if and only if (J. = /3, as
r1 = nc;l L X(~)(g)[X<P)(g)]*1 = b~p . (2.3.10)
g
A vector transforming according to the identity irrep III the space L =

x Da) is
L(~)
(2.3.11)
el~) and el~) being the bases in the spaces of irreps 15(~) and D(~) respectively.
Consider now the (outer) direct product of a rep on itself (square of a
representation):
I D(g) = D(~)(g) x D(~)(g) , I (2.3.12)
with the character
(2.3.13)
Let Vi and Wj (i,j = 1,2, ... , n~) be two linearly independent sets of basis vectors
spanning the space of the irrep 15(~). The space L of the direct product (2.3.12)
of irreps is formed by n;
vectors viwj. It may be split up into two invariant
subspaces L + and L - spanned by the vectors Uif = viwj VjWi symmetrical and
antisymmetrical with respect to the permutation of indexes i and j respectively.
In fact
(2.3.14)
We rewrite this relation interchanging the indexes i' andj'. Summing the result
with (2.3.14) and dividing by two, one obtains
15(g) UiT = L (1/2) [Dl~l(g)Djry)(g) Dj~)(g)D[y(g)] Ui~' (2.3.15)

i'j'
The character of the reps in the spaces with bases Uif are
x(g) = L (1/2) [D[i)(g)Dj~)(g) Dji)(g)D~)(g)]

ij
(2.3.16)
The vectors Ui; = ~-:- = viwj + VjWi are said to transform according to the
symmetrical square of the irrep D(~)(g). Its character is denoted by [X(~)]2(g) and
is equal to
(2.3.17)
The dimension of this rep is na(na + 1)/2.

The vectors, antisymmetrical with respect to the permutation of indexes i, j,
Ui; = - ~i = ViWj - VjWi form the basis of an na(na - 1)/2-dimensional rep
which is called the antisymmetrical square of an irrep D(a)(g). Its character is
denoted by {la)V(g) and is equal to
(2.3.18)
If the basis functions of the direct product D(a) x D(a) are constructed with
the help of only one set of vectors Vj (Uij = vivj) then it is impossible to generate
vectors which are antisymmetrical with respect to exchange of the indexes. The
products vivj are themselves symmetric. The number of such linearly indepen-
dent products is na(na + 1)/2. They transform according to the symmetrical
square of the irrep D(a)(g) with the characters (2.3.17).
2.3.2 Subduction of Representations

Let fj(g) be a rep of a group G (g E G). A set of operators fj(h) (h E H c G) is a
rep of H subduced by rep fj(g) of G. It is convenient to denote this fjtH. Even
if fj(g) = fj(a)(g) (g E G) is an irrep of G the subduced rep is in general reducible
and may be decomposed into irreps dry) of H
(2.3.19)
The multiplicities are obviously equal to
r~a) = nil I la)(h) [X(Y)(h)] * , (2.3.20)

h
where X(a)(h) and X(Y)(h) are the characters of irreps D(a)(g) and d(Y)(h) of the
groups G and H c G respectively.
Let vJa) be the orthonormal basis of irrep D(a)(g) of G and e!V be the
orthonormal bases of irreps d(Y)(h) of its subgroup H contained in D(a) tH. The
index p distinguishes the independent bases of equivalent reps')' for r~a) > 1.
Obviously
e(y)
ip
_
-
"( '1 . )Vj(a) ,
L, IX,) ,)" I, P (2.3.21)
j
vJa) = L (a,jly, i, p)*el~ , (2.3.22)

yip
where (a,jly, i,p) are the reduction coefficients forming a unitary matrix in which
the indexes j and (y, i, p) label rows and columns, respectively.
The application of the operator Pi\r) to the basis vector vJ~) gives the vector
e~Y)
IP
= (NO)-1/2 p.<'r)v~~)
U J
= (No )-1/2(n y/n H ) L (dlr)(h* Djp (h) vya) (2.3.23)

hj
Comparing (2.3.23) with (2.3.21) we obtain for the reduction coefficients
(2.3.24)
As it follows from the property of the operator Pi\r) the sum in (2.3.24) becomes
zero if the vector vJa) does not contain el~. The numbers j' and i' are assumed to
be chosen so that the sum (2.3.24) is nonzero. This choice ofj' and i' determines
the reduction matrix column which corresponds to p = 1. The normalizing fac-
tor (Notl/2 is calculated using the condition (el~, e!~) = 1:
No = L (ny/nHf L (dlr>(h'*D 7)(h') x d!P(h)(DjP(h*
j (2.3.25)
j hh'
But
L (D 7)(h*DH)(h') =
j Dj:'}(h- 1 h') , (2.3.26)
j
After inserting (2.3,26) into (2.3,25) we replace the summation over h' by the
summation over h" = h- 1 h'(h' = hh"):
No = (n y/n H )2 L (dlr)(hh"*dlr>(h)Dj~l(h")
hh"
. (2.3,27)
Writing out d!r)(hh") through the product of matrices and using the ortho-
gonality relation (2.2.19) we obtain finally
(2.3.28)
As is seen from (2.3.28), the normalization factor (Notl/2 is the same for all
the reduction matrix columns with different i and fixed y and p.
The choice of other j' and j' in (2.3.23) will give a zero result, or linearly
dependent columns, or linearly independent columns (for r~a) > 1) with earlier
found columns. In the latter case these columns may be taken as elements of
the reduction matrix A with p = 2 provided that they are orthogonal to the
columns with p = 1. Otherwise this orthogonalization has to be done using
Schmidt's procedure. In the latter, it is sufficient to determine the orthogonaliza-

tion coefficients only for i = 1. For other columns they will be the same. The
other values j' are chosen up to p = r~a). The procedure is the same for the
columns corresponding to other irreps d(Y)(h) contained in D(a) tHo
Usually all the information about the decompositions (2.3.19) for a given
group G and its subgroups H is given in a correlation table. Its rows are labeled
by the symbols of G group irreps and its columns by the symbols of H c G
groups. The members of the decomposition (2.3.19) are at the intersections of
the D(a) rows and H columns in this table.
2.3.3 Induction of Representations

Let G be a group and H be its subgroup. The group G is assumed to be decom-
posed into left cosets with respect to H
gl = E , (2.3.29)
The set of elements
(2.3.30)
is a group H(j) c G isomorphous to H. Multiplying (2.3.29) from the right side

by gj-1, the group G is partitioned as follows:
(2.3.31)
This is a decomposition of the group G into left co sets with respect to the
subgroup H(j), where gj"gj-1 are the left coset representatives. The relation
(2.3.31) also shows that any element of G can be represented as a product
hEH, (2.3.32)
Now let L be a linear vector space of some rep of a group G. It is also a rep
of its subgroup H. Let Vl) c L be a subspace of L with the basis vectors eW
(i = 1,2, ... , ny) transforming according to an irrep d(Y)(h) of H:
D(h)eW = L di'i(h)e?l
i'
, i = 1, 2, ... , ny . (2.3.33)
To express the invariance of L(1) under D(h) (h E H) independently of a particu-

lar choice of basis vectors we write
(2.3.34)
Consider the set of vectors
e(Y)
IJ
= D(g.)e(Y
J I1
)
,
j = 1,2, ... , t , i = 1, 2, ... ,ny , (2.3.35)
where gj are the coset representatives in the decomposition (2.3.29). The vectors
(2.3.35) are assumed to be linearly independent. The vectors (2.3.35) with a fixed
j form a space L(j). The operator i5(g) maps the space L(l) onto the space L(j)
i5(gj)L(l) = L(j) . (2.3.36)
The set of n = tny vectors (2.3.35) span a space

Ln = L L(j) (2.3.37)
j
which is invariant under the operators i5(g) (g E G). Indeed, according to (2.3.32)
and (2.3.34, 36)
i5(g)L(j) = i5(gj" )i5(h)i5- 1 (gj)Vj)
(2.3.38)
Therefore Ln is a space of the group G rep induced by the irrep d(Y) of its
subgroup H and written as d(Y)iG. Its dimension is n = tny- It is easy to write the
matrices of the induced rep d(Y)iG in the basis (2.3.35) of Ln. With the help of
(2.3.32, 33) we have
= L d!rl(h)e!1" . (2.3.39)
i'
We rewrite (2.3.39) in the form
(2.3.40)
where
(2.3.41)
Thus the matrices D[YJ(g) of induced rep d(Y)iG have a block structure.
Nonzero blocks are matrices of the irrep d(Y) of H. Every row and every column
of D[YJ(g) has only one nonzero block. As is seen from (2.3.41), the trace of the
jth diagonal block is equal to
_ [yJ _ {O, H;
if gj-l ggj 1.
(2.3.42)
Xj (g) - iY)(h), if gj-l ggj = hE H ,
and therefore the character of the induced rep is
X(g) = LXyl(g). (2.3.43)

j
To transform (2.3.43) let us denote by ns the order of a class S in G and by ns the

order of a class s in H. A class s in H is either not contained in a class S of G or
is contained once as a whole. Every element of a class S is repeated nG/nH times
in a set of nG elements g-l gg (g runs over G). Hence the set of elements g-l gg
either contains nsnG/ns elements of class s (if s c S) or does not contain them at
all (if s S).
If gj-l ggj = h E H, then
(2.3.44)
i.e., each of the nH elements of the left coset gjH generates an element of the class
s in the set g-l gg for g = gjh, if s c S. Therefore the number of elements of class
s in the set of t = nG/nH elements is equal to
(nons)/(nHnS) , if s C S
(2.3.45)
0, ifs S .
Taking this into account, (2.3.43) may be rewritten in the form
Xs[Y] = /n n '\' n X(Y)

nGHSL.ss' (2.3.46)
SES
where X~Y) and X~] denote the characters of class s elements in the irrep dey) of H
and of class S elements in the induced rep d(Y)jG of G, respectively, and the sum
is taken over the classes of H contained in the class S of G.
In the general case, a rep d(Y)jG is reducible
d(Y)jG = I r~Y]D(")(g) . (2.3.47)

a
The multiplicities of irreps D(a)(g) in d(Y)jG may be found in the usual way
r~Y] = nG l I x[Y](g)(x(a)(g))*
9
(2.3.48)
Using (2.3.46) we have
= n-HL.ss
1 '\' n x(y)(x(a)* = rea)
S Y' (2.3.49)
i.e., the multiplicity of an irrep D(a)(g) of G in a rep d(Y)j G induced by an irrep dey)
of H eGis equal to the multiplicity of an irrep dey) of H in the rep D(a)!H

subduced by D(a) on H. This is the Frobenius reciprocity theorem.
Let us define v~~ to be a symmetry-adapted basis in the space of the induced
rep d(Y)jG. This basis is related to the basis (2.3.35) by a unitary transformation
(reduction matrix)
v~~ = L (yijllXkp)elY
ij
(2.3.50)
Applying the operator P~k! (2.2.32) to the basis vector elrl we obtain vial to within
a normalization factor N- 1/ 2 :
V eal - N- 1/2 p,(a)e(Y)
kp - kk' i'l
= N- 1/2 (n a /n G ) L (Dkk\(g* DfJill (g)elY

gij
(2.3.51)
By comparing (2.3.50) and (2.3.51), the elements of the reduction matrix can be
written as
(yijllXkp) = N- 1/2(n a/nG) L (Dkk\(g* DfJ;l1 (g) . (2.3.52)

9
Indexes i' and k' are assumed to be chosen in such a way that the vector (2.3.51)
is nonzero, i.e., Vk~~ is contained in elrl. The calculation of the normalization
factor N is analogous to that for the reduction matrix of a subduced rep
(2.3.25-28):
N = (na/nG) L (DW(g*DWl(g)
9
. (2.3.53)
Since, according to the decomposition (2.3.29), g = gjh, the summation over

g E G in (2.3.53) may be replaced by the summation over h E H and over left
coset representatives (over j from 1 to t). We also use (2.3.41) and (2.3.28) for
the normalization factor No of the symmetry-adapted vectors when subducing
D(a)!H:
N = (na/nG) L (Dkk)(gjh*ii 1j dlr)(gjh)
jh
(2.3.54)
Analogously, using (2.3.24, 54) we find the relation between reduction ma-
trices during induction and subduction
(yijllXkp) = N- 1/2 (n a /n G ) L (Dkk\(gjh*dli>(h)

h
(2.3.55)
For j = 1 (2.3.55) becomes
(yi1Icxkp) = (n"nH/nGny)1/2(cxklyip)* , (2.3.56)

so that
(Yiilcxkp) = I(m~\(g)*(yillcxk'p) . (2.3.57)
k'
Thus, the reduction matrix coefficients of the G group rep induced by an

irrep d(Y) of its subgroup H are determined by the reduction matrix coefficients
of the restriction of irreps D(") of G to elements of H and by matrix coefficients
of the irreps D(<X) themselves for elements gj (2.3.55). The reduction matrix coeffi-
cients of the first block row are especially simple to calculate (2.3.56). The coeffi-
cients of other block rows are expressed simply through the coefficients of the
first block row (2.3.57).
Consider a special case when the G group irrep matrices have a completely
reduced form for the elements h E H c G, Now it is convenient to label the rows
and columns of the matrices with the help of three indexes, the sense of which is
clear from the preceding discussion (k' --+ y' i' p'). The reduction matrix is then
diagonal
(cx(y'i'p')lyip) = Dyy,Dii,Dpp' (2.3.58)
Now instead of (2.3.55) we have
(yijlcx(y' i' p')p) = (n<xnH/nGny)1/2(D~~I'p'Yip(g)* (2.3.59)
In particular, the reduction matrix coefficients of the first block row (j = 1) are
equal to
(2.3.60)
2.3.4 Little Group Method of Irreducible Representation Generation

Let H be an invariant subgroup of a group G (H <J G). We develop G in terms
of left cosets with respect to H:
91 = E . (2.3.61)
Consider an irrep D(<X)(g) of G in a space L and its restriction D(<X)!H to

elements of H. The latter is, in general, reducible and may be decomposed into
irreps of H:
D(")!H = I rpd(P)(h) . (2.3.62)

p
Let
(i = 1,2, ... , np, p = 1,2, ... , rp) (2.3.63)
be the basis vectors of the irreps dIP) which appear in D(a) !H:
he!!) = D(h)e!!) = L d!Pl(h)eIP~

i'
. (2.3.64)
The vectors gje!!) (i = 1,2, ... , np, for fixed j and p) span the space of an irrep of
the group H. Indeed
(2.3.65)
The irreducibility of the rep d(Pj)(h) = d(P)(iij- 1 hii) is a consequence of the

irreducibility of the rep dIPl(h). The matrices d(Pj)(h) = d(P)(iJj-l hii) form an irrep
of dimension np which is said to be conjugate to d(P)(h) by means of iij . This rep
may be either equivalent or inequivalent to rep d(P)(h).
Let us pick out of the set of the representatives iij in the decomposition
(2.3.61) those elements qu (u = 1,2, ... , m) which generate reps d(P)(q;;l hqJ equiv-
alent to d(P)(h):
(2.3.66)
The set of elements
hEH, u = 1,2, ... , m , (2.3.67)
is closed with respect to the composition law of G. Hence, it is a group Q(P) c G

of order nQ = mn H called the little group for an irrep dIP) of He G. It is evident
that the following partition of Q(P) with respect to H <J Q(P) holds:
ql = E 1 (2.3.68)
The basis vectors e!!) (i = 1,2, ... ,n p,p = 1,2, ... ,rp) span the space Lll) being
invariant under Q(P) and, as we shall see, irreducible.
Now the group G may be decomposed into left cosets with respect to
Q(P) c G:
gl = E. (2.3.69)
The vectors gA!) for fixed j =f. 1, {3, p span the space of an irrep d(Pj) of H
conjugate but inequivalent to d(P)(h) (otherwise gj E Q(P). The set of vectors gje\V
distinguished by p for fixed j i= 1, 13 transforms according to the same irrep
for j i= 1 . I (2.3.70)
Let us denote by L(j) the space spanned by nprp linearly independent vectors
gje (.1- - 1, 2, ... ,np,p-
- 1, 2, ... ,rp),
,
ip
(P)
j = 1 2, ... , nG/nQ (2.3.71)
Any element of the coset gjQ(P) maps Vl) into Vj). The spaces Vj) are linearly
independent because they transform according to inequivalent reps of H. The
direct sum of L(j) is a space L= LjL(j) invariant under G. This is the space of the
irrep D(a) introduced at the beginning of this section.
Now we can prove the irreducibility of the rep of Q(P) in the space L(l).
Indeed, there is no subspace of smaller dimension IY) invariant under Q(Pl.
Otherwise the direct sum
l= L gjDl) (2.3.72)
j
would be a subspace of L (l c L) invariant under G, which contradicts the

initial assumption of irreducibility of L.
A set of conjugate inequivalent irreps d(P j) (j = 1,2, ... , nG/nQ) of H con-
tained in the subduced rep D(a)!H is called a star (or orbit) of d(P) and is denoted
as *13. As we have seen, all the irreps d(Pj) of a star have the same dimension np
and are contained the same number of times rp in D(a) !H.
The vectors el~) (i = 1,2, ... , n p, p = 1,2, ... , rp) span the space L(l) of an
irrep of the little group Q(P)
- "D(P)
, (P) -
qeip L.. i'p'ip () (P)
q ei,p' , q E Q(P) . (2.3.73)
i'p'
The group Q(P) is uniquely determined by an irrep 13 of H <J G and has H as an

invariant subgroup. The groups QJP) = gjQ(P)gXl with elements q(j) = gjqgj-l
[q E Q(P), gj being representatives in the decomposition (2.3.69)] are isomor-
phous to Q(P). The vectors gjel~) transform according to an irrep of QJP):
q(j)(gjel~) = (gjqgj-l )gA~) = L DjPJ,iiq)gjeWJ,

i'p'
= L...
" D~Pj).
,'p',p
(q(j))g'J.e!P)
.'p' , (2.3.74)
i'p'
with the rep matrices
(2.3.75)
In particular, for q = hE H the matrix D(P) in (2.3.73) and (2.3.75) has a quasi-
diagonal form with the matrix d(P)(h) on the main diagonal repeated rp times.
The spaces LV> in (2.3.71) are linearly independent and transform according
to inequivalent reps of H. The irrep D(Il)(g) of Gin L appears to be induced by
an irrep D(P) of the little group Q(P) c G. In the basis
i = 1,2, ... , np , p = 1,2, ... , r p ,
(2.3.76)
the matrices of this irrep have a block structure [see (2.3.41)J
[Pl
Di'p'j'ipj ()
9 -- D(P) (-1 ) ~
i'p'ip gj" qgj Uj'j" (2.3.77)
So the irrep D[Pl of G is induced by the irrep of a little group Q(P) which, when
restricted to H, contains rp times only an irrep d(P) of H. These irreps of Q(P) are
called small irreps (allowed, permitted).
As we see, any irrep of a group G is related to some star of conjugate irreps
of its invariant subgroup H. Anyone of the members of a star *13 (e.g., rep 13
itself) uniquely determines a little group Q({i). Every small irrep of the little
group Q(P) induces an irrep of G. Using all the stars of H <J G and all the small
irreps of corresponding little groups we obtain all the irreps of G.
The representatives qu in the expansion (2.3.68) do not, in general, form a
group. The product of any two of them is equal to a member of some left coset
but may not be its representative:
(2.3.78)
The multipliers hus are fixed for any pair of representatives and satisfy the
relation
(2.3.79)
The latter relation is a consequence of the associativity of group multiplication
(2.3.80)
In a small irrep of Q(P) the relations (2.3.78, 79) map the following matrix
relations:
(2.3.81)
(2.3.82)
Let any left coset quH of the factor group Q(P)/H be mapped by a matrix
D(qu)' The set of matrices D(qu) is not a rep of Q(P)/H since the correspondence
between qH and D(q) is not conserved in the composition law (2.3.81). The
problem is to find the matrices D(qJ satisfying the relation (2.3.81) where the
matrices D(h us ) are assumed to be known. They are matrices of an irrep d(P)(hus )
of H or quasi-diagonal matrices with blocks d(fJ)(h us ) repeated rp times on the
main diagonal.
In the case of a one-dimensional irrep d(fJ) of H the matrices D(P)(h us ) are
(2.3.83)
where w(u,s) = X(P)(h u.) is a complex number and Iw(u,sW = 1. In this case
(2.3.81,82) are replaced by
D(qJD(qs) = D(qu.)w(u, s) , 1w(u, s)1 = 1 (2.3.84)
w(us, r)w(u, s) = w(u, sr)w(s, r) . (2.3.85)
A set of matrices D(qu) with multiplication law (2.3.84) is called the projec-
tive rep of the factor group Q(P)/H with a factor system w(u, s). For a finite group
the number of inequivalent factor systems is finite. If w = 1 for all pairs qu, qs the
projective rep coincides with the usual one. For example, this is the case for a
group when the representatives of left cosets in (2.3.68) themselves form a group
Q and Q(P) is a semi-direct product of its subgroups H <J Q(P) and Q,
Q(fJ) = H 1\ Q. (2.3.86)
This is also the case for an identity irrep of H, when the connection between
small irreps oflittle group Q(P) and irreps of the factor group Q(P)/H is especially
simple. Any irrep of Q(P)/H generates some small irrep of the little group Q(P). In
this irrep all elements of a left coset quH of Q(fJ) are mapped by the same
matrix n(fJ)(qu) of the element quH in the corresponding irrep of the factor
group Q(fJ) / H. In particular, the unity matrix corresponds to all elements of
H (they are mapped by the identity element of Q(fJ) / H).
In contrast, the set of Q(fJ) irreps in which the identity matrix corresponds to
all elements of H generates all the irreps of the factor-group Q(P)/H. In these
irreps the same matrix corresponds to all elements of the left coset quH. It is
precisely this matrix which corresponds to the left coset quH of the factor group
Q(P)/H.
3. Symmetry Groups and Their Representations
The investigation of atoms, molecules and crystals involves the analysis of their symmetry groups:
full orthogonal groups for atoms, point symmetry groups for molecules, and space groups for
crystals. All these groups are subgroups of the same continuous group: the Euclidean group. In the
following sections we give, briefly, the most important information about these groups. Special
attention is paid to site symmetry of physical systems related to the subgroups of a symmetry group.
3.1 The Euclidean Group and Its Subgroups
The elements of the Euclidean group E3 are operations in three-dimensional

space that leave the distance between any two points unchanged. By definition
the product of two successive operations is an operation, which has the same
result. The set of all such operations is closed with respect to the composition
law and satisfies all the requirements of the definition of a group.
Let the basis vectors of a Cartesian coordinate system ei (i = 1,2,3) be
directed along axes X = Xl' Y = X 2 , Z = X 3 . Any point of the space is charac-
terized by a radius vector r with Euclidean coordinates Xi (i = 1,2,3). A set of
vectors corresponding to all points of the space forms a linear vector space L. A
point with a radius vector r will occupy, under Euclidean operation, a new posi-
tion r' with respect to the chosen coordinate system. Hence, every Euclidean opera-
tion is mapped onto some transformation (operator) in the three-dimensional
space. These operators form a group isomorphous to the group of the Euclidean
operations which is also called Euclidean.
3.1.1 Translation Group
The set of translational operations of three-dimensional space is closed with

respect to the multiplication law and forms a translation group T. A translation
is characterized by a vector
(3.1.1)
determining the magnitude and the direction of translation. The corresponding

transformation (operator t.) in L3 is

32 3. Symmetry Groups and Their Representations
r' = t"r = r +a ; (3.1.2)

i = 1,2,3 (3.1.3)
The composition law in Tis
It", t"2 = t", +"2 . I (3.1.4)
Hence T is a commutative group. The operators t" are nonlinear.
3.1.2 Rotation Group

Now consider the operations that leave one point of the space stationary. For
example, these can be rotations about different axes passing through one fixed
point O. Every rotation may be characterized by a vector p. Its direction
determines the orientation of the rotation axis in the space and its length is
equal to the rotation angle about this axis. We let anti-clockwise rotation corre-
spond to the positive direction of the vector p. The rotation through an angle p
about an axis is equivalent to the rotation through the angle - p about an axis
in the opposite direction. Therefore, it is sufficient to consider only vectors p
with p < n. When p = n the vectors p and - p correspond to the same rotation.
The set of all rotations p forms the rotation group 0+(3), the elements of
which are denoted by R(fJ) or, in short, R. We write the transformation of
position vectors under rotation R(fJ) in the form
I r' = R(fJ)r . I (3.1.5)
It is obvious that
(3.1.6)
i.e., the operator R(P) is linear. In the basis ei(i= 1,2,3) the rotation opera-
tor is equivalent to a matrix D(P)
(3.1. 7)
(3.1.8)
The matrix D(fJ) determines the transformation of Cartesian coordinates of

position vectors
x;, = L Di'i(fJ)X i (3.1.9)

i
3.1 The Euclidean Group and Its Subgroups 33
Rotations leave distances (lengths of position vectors) and angles between

radius vectors of any two points r 1 and r 2 unchanged and, therefore, the scalar
product of vectors r 1 and r2:
(3.1.10)
It follows from (3.1.10) and the realness of 3-dimensional space that the opera-
tors R(fJ) and matrices D(fJ) are orthogonal.
Under rotation R(fJ) a cube of unit volume constructed on three vectors ei
changes its orientation in the space without any change in its volume. Hence
(3.1.11)
So every rotation R(fJ) is related to an orthogonal transformation of Cartesian

coordinates with determinant 1. The converse is also true, which is proved
by a direct calculation of the scalar product (r~, r~) and scalar triple product
(e~ [e; x e;]).
An arbitrary rotation is characterized by a vector p, i.e., by three real
parameters (e.g., by Cartesian coordinates Px, PY' pz of fJ). Another widely used
choice of three rotation parameters is the set of Euler angles, which are defined
as follows. The space is assumed to be rigidly attached to a coordinate system
X', Y', Z' with axes along e; (i = 1,2,3). Thus, under rotation the moving system
of axes X'Y'Z' changes its orientation with respect to the fixed system of refer-
ence XYZ with axes along ei . A rotation R E 0+(3) is considered to be a succes-
sion of three rotations: first a rotation of the space (reference system X'Y'Z')
through an angle <p about the Z-axis, then a rotation through an angle 9 about
the X-axis and lastly a rotation by an angle t/I about the Z-axis (Fig. 3.1). The
planes XOY and X'OY' intersect along the line (of nodes) ON. As is seen from
Fig. 3.1, <p = LNOX', t/I = LXON, 9 = LZOZ'.
The relation between the Cartesian coordinates Px, PY' pz of the rotation
vector p and the Euler angles <p, 9, t/I is
z
z'
y'
)r-==----+-r-y
x
N Fig. 3.1. Euler angles cp, 9, 1/1
a = exp[ -i(I/I + <p)/2J cos(.9/2)

= cos(f3/2) - i(f3z/f3) sin(f3/2) ,
(3.1.12)
b = -iexp[ -i(I/I - <p)/2Jcos(9/2)
= - [(f3y + if3J/f3J sin(f3/2) .

101 2 + Ibl 2 = 1 . (3.1.13)
The two complex numbers a and b (Cayley-Klein parameters) satisfying

(3.1.13) also give three real parameters determining a rotation.
The components of the rotation matrix D (3.1.8) may be written as a func-
tion of any three rotation parameters. This matrix expressed in terms of f3x,
f3y, f3z is
O,f3<n. (3.1.14)
Let us define a class of mutually conjugate elements in the rotation group
R(P') = RR(P)R- 1 , (3.1.15)
Let D(P) be a matrix in a basis ei (i = 1,2,3),
(3.1.16)
The matrix D'(J!) in the basis e; = Rei (ei = R- 1 e;)
R(p')e; = RR(P)R -1 e; = L Di'i(p)e;

i'
= L D;'i(p')e;
i'
(3.1.17)
coincides with the matrix D(P) in the basis e i , i.e., the vector p' has the same
orientation with respect to e; as the vector p with respect to ei' But the basis e;
was subjected to a rotation p relative to the basis ei Hence the vector p' arises
out of the vector p by the rotation R
p'=Rp. (3.1.18)
Since under rotation the lengths of vectors do not change, all rotations by the
same angle about all possible axes through a fixed point are in one class
I RR(fI)R- 1 = R(RfI) (3.1.19)
3.1.3 Inversion Group

By definition, an inversion about the center of a reference system is an operator
I,
Ir = -r ; lei = e; = -e i ; (3.1.20)
The linearity of the operator I is obvious. In any basis it is related to the matrix
D(J) = [- ~ ~ ~l
- (3.1.21)
o 0-1
with the determinant - 1.

The operators E and I form a group of second order which is called the
inversion group. It is denoted Ci . Under inversion a right set of vectors ei is
transformed into a left one e; = -e i. There is no rotation which puts e i and e;
in coincidence. As
Rlr = R( -r) = -Rr = IRr (3.1.22)
for any r, then
I IR = RI , (3.1.23)
i.e., the inversion of space commutes with any rotation. The commutativity of
the corresponding matrices is obvious, since the inversion matrix is a multiple
of a unit matrix.
3.1.4 Full Orthogonal Group

The full orthogonal group 0(3) contains all the elements R E 0+(3) and their
products with the inversion RI = I R. The rotation and inversion groups are
both invariant in 0(3). The latter may be expressed as a direct product of these
two:
0(3) = 0+(3) x Ci (3.1.24)
The elements R E 0+(3) are called proper rotations. The matrices mapping the
elements of a rotation group have the determinant 1. The elements RI are called
improper rotations and matrices mapping them have the determinant - 1. The
full group of (proper and improper) rotations is isomorphous with a group of
orthogonal matrices. That is why the group is called full orthogonal.
1 IR(nw) = o-(w) 1 (3.1.25)
(w = PIP is a unit vector determining the direction of the rotation axis) is a

reflection in a plane perpendicular to w (mirror reflection plane). Any im-
proper rotation may be written in the form
IRn + a)w) = IR(nw)R(aw) = o-(w)R(aw) = S(aw) , (3.1.26)
i.e., as a rotation through an angle r:t. about an axis w combined with a reflection
in a plane perpendicular to the rotation axis [mirror rotation S(r:t.w)]. The
elements of the full orthogonal group are said to be rotations and mirror rota-
tions. A reflection in a plane may be considered as a mirror rotation through the
angle zero
o-(w) = S(Ow) . (3.1.27)
To obtain all conjugate elements of a rotation R(fJ) in the group 0(3) it is

necessary, to consider besides (3.1.19) also the elements
1 IRR(fJ)(RI)-l = RR(fJ)R- 1 = R(RfJ) = R( -IRfJ) 1 (3.1.28)
Thus, the improper rotations in 0(3) do not generate new elements in the
conjugacy class relative to the rotation group 0+(3). It may be proved in the
same way that
RS(fJ)R- 1 = S(RfJ) , (3.1.29)
(IR)S(fJ)(IRfl = S( -IRfJ) . (3.1.30)
Therefore, in the full orthogonal group, (a) rotations through a fixed angle
about all axes are mutually conjugate; (b) improper rotations by a fixed angle
about all mirror axes are members of the same conjugacy class.
The group 0(3) is a symmetry group of atoms.
3.1.5 Euclidean Group

The Euclidean group E3 is composed of elements R of the full orthogonal group
0(3), of elements of the translation group T and of all their products. Any
element g of E3 may be written as
Ig = (Ria) = t"R . I (3.1.31)
i.e., as a combined operation: a rotation R (proper or improper) followed by

translation over a vector a. In the notation of (3.1.31) the elements of 0(3) and
T have the forms (RIO) and (Ela) respectively. An element g transforms a point
r of the space into the point
r' = (Rla)r = Rr +a , (3.1.32)
or
xi = IPii,(R)x i , + ai (3.1.33)
i'
The operator (Ria) is not linear (for a *- 0).

To obtain a formal composition law for elements of E3 let us find the
position of a point r after two successive Euclidean operations
(3.1.34)
Thus,
(3.1.35)
In particular, for (R 2 Ia 2 ) = (R1Iatl- 1 the product (3.1.35) is equal to the identity

element (EIO):
and (3.1.36)
Hence
(R1Iatl- 1 = (Rl11-Rl 1a 1) . (3.1.37)
The element conjugate to (Ria) by (Rid) E E3 is
(3.1.38)
For pure translations (R = E) we have
(3.1.39)
Since IRal = lal = a, all translations with the same length of translation vector
are contained in a single conjugacy class. Another consequence of(3.1.39) is that
the translation group is a normal subgroup in E3 and the latter is a semi-direct
product of T and 0(3):
E3 = T /\ 0(3) . (3.1.40)
For a = 0 and R= E the relation (3.1.38) becomes
(Eld)(RIO)(Eld)-l = (Rid - Rd) . (3.1.41 )
Let R = Ro be a proper or improper rotation about an axis passing through the

point O. The operation in the left-hand side of (3.1.41) may be regarded as the
same rotation but about an axis passing through the point 0' located a distance
d from the point 0 (Fig. 3.2):
(Rold - Rod) = (Ro,IO) , (3.1.42)
or, after multiplying both sides of (3.1.42) from the left by the translation
(Ela - d + Rod),
I (Rola) = (Ro,la + Rod - d) (3.1.43)
This relation shows that a motion of the space may be represented as rotations
about axes of the same direction but passing through different points (0 and 0').
The displacement of an axis by a vector d from a point 0 to a point 0' has to be
accompanied by the addition to the translation a of the supplementary transla-
tion Rod - d.
Let RoUI) be a proper rotation about an axis passing through a fixed point
o and a.1 be a translation vector perpendicular to the rotation .axis: (p. a.1) = O.
Then the operation (RoU/)la.1) with (a.1 . fJ) = 0 is a pure rotation (Ro,UJ)IO) about
an axis translation ally displaced over a vector d such that a.1 = d - R(P)d
(d = a.1/[2sin({3/2)], (a.1:d) = (n - {3)/2 (Fig. 3.2).
Now let all be a translation vector parallel to a rotation axis (P x all = 0).
The element (Ro(fJ)lall) E E3 is a screw rotation about a screw rotation axis.
It is obvious that an element (Ro(p)la) with a = all + a.1 is a screw rotation
(Ro,(P)lall)' Further, let Ro(P) = O"o(w) be a reflection in a plane containing a
~ ____ ~ ________ ~O'
Fig. 3.2. Supplementary translation caused by the displace-

ment of a symmetry element from the point 0 to the point 0'
3.2 Point Symmetry Groups 39
fixed point O. As (Jod - d = (Jod l - d l = - 2d l (d li l m) it is sufficient to consider

only vectors d = d ll perpendicular to the plane displaced in the space by the
vector d l = a 11/2. An element of symmetry (J( m) Ia.L) with P .l a.L is called a glide
reflection plane. It is a reflection in a plane combined with a translation a.L in
the plane itself. In the general case an element (Jo(m) Ia) with a = all + a.L is also
a glide reflection operation (Jo(m) Ia.L)'
Consider now a mirror rotation So(P} accompanied by an arbitrary transla-
tion a = a.L + all (P = 13m)
(So(p}la) = (Elall)(JO(m)IO)(Ela.L)(Ro(P)IO)
= (JO(m)lall)(Ro(P}la.L)
= (Jo(m)IO)(Ro(P}IO) = (So(P}IO) (3.1.44)
This is a mirror rotation with respect to a displaced point of symmetry.
Thus the Euclidean group contains elements of five different types: transla-
tions, proper rotations, improper rotations, screw rotations, glide plane reflec-
tions.
3.2 Point Symmetry Groups
Molecules consist of positively charged nuclei and negatively charged electrons

moving around them. If the translations and rotations of a molecule as a whole
are excluded, then the motion of the nuclei, except for some special cases,
consists of small vibrations about their equilibrium positions. Orthogonal
operations that transform the equilibrium configuration of the nuclei of a mole-
cule into itself are called the symmetry operations of the molecule. They form
a group G of molecular symmetry. The groups G are subgroups of the full
orthogonal group and are named the point symmetry groups, since operations
from G keep one point of the space fixed. All the symmetry planes and axes
intersect at this point. Thirty-two point groups are used in the symmetry theory
of perfect crystals and crystals with point defects. These are the so-called
crystallographic point groups.
3.2.1 Symmetry Elements of Molecules and Crystallographic Point Groups

Let us consider some definitions, notations and useful relations for elements of
point symmetry groups [3.1].
The rotations about an n-fold axis Cn through multiplies of the angle 2nln
are denoted by C!. If such rotations are combined with a reflection in the plane
perpendicular to the rotation axis one is dealing with an n-fold mirror rotation
axis denoted by Sn. The axis of highest possible order n, if it is unique in the
system, is named the principal axis. It is assumed to point in the z-direction.
Usually the following notations are used for the symmetry elements:
U -two-fold rotation axes perpendicular to the principal symmetry axis;
ah(az ) -a reflection plane perpendicular to the principal symmetry axis;
av -reflection planes containing the principal axis;
ad -reflection planes containing the principal axis
if they bisect the angle between neighboring two-fold axes U.
The axes are said to be equivalent if the point group contains an operation
transforming one axis into another. In the full orthogonal group all axes are
equivalent. This is not true for the point groups.
According to (3.1.19, 28-30) rotations (mirror rotations) through the same
angle about equivalent axes are in the same class. Remember that the reflection
in a plane may be regarded as a mirror rotation through zero angle. An axis is
called bilateral if rotations C! and C;;k (S! and Sn- k) are conjugate. An axis
w = PIP is bilateral if RP = -P or -IRP = -P [IRP = p, see (3.1.19, 28-30)J,
i.e., if the point group contains a rotation by the angle n about an axis perpen-
dicular to w, or a reflection plane containing the axis w.
The main designations of point groups are given in Table 3.1. For molecules
the Schonflies notation (abbreviated "Sch" in the table) for these groups is
used. In describing crystal symmetry the international notation (or Hermann-
Mauguin notation) is also of use. In the latter the point group notation is
determined from the principal symmetry elements of the group: an n-fold axis
is denoted by the symbol n, a reflection mirror plane by the symbol m. The
symbols nlm and nm are used for the combinations of an n-fold axis with the
reflection plane perpendicular to the axis or containing the axis, respectively.
Instead of mirror rotation axes, the international system uses inversion axes n
when a rotation through an angle 2n/n is followed by the inversion operation.
The full international notation of a point group consists of the symbols of group
generators. Abbreviated international notations are also used. The international
notations of the groups Cnh , Cnv , D n , Dnh are given first for even n and then for
odd n.
Linear molecules have continuous symmetry groups Coov and Dooh which
may be obtained as the limiting cases of the point groups Cnv and Dnh for n -+ 00.
3.2.2 Site Symmetry Subgroups of Point Groups

Atoms in a molecule occupy the positions q with a certain site symmetry de-
scribed by some subgroups G, of the full symmetry group G of a molecule. The
central atom (if one exists) has a site symmetry group G, = G. Any atom on the
principal symmetry axis of molecules with the symmetry groups Cn and Cnv also
has the full symmetry of the molecule (G, = G). Finally, G, = G for any atom
lying in the symmetry plane of a molecule with the symmetry group G = Cs In
other cases G, c G and includes those elements REG that satisfy the condition
Rq= q.
Let G1 be a site symmetry group of a point ql in the molecular space. This
point may not be occupied by an atom. Let the symmetry group G of a molecule
be decomposed into left cosets with respect to its site subgroup G1
3.2 Point Symmetry Groups 41
Table 3.1. Point symmetry groups
Group G symbol nG Symmetry Generators and kG Remarks

Sch International element generating relations
Cn n n n Cn a = Cn; an = E. n
n+6
CnL. nmm nmm 2n en, nav a = en, b = a v ; an = E, --
2
n+3
nm nm b 2 = E, ba = an-lb. - -
2
S2n i'i i'i 2n S2n a = S2n; a 2n = E. 2n S2 = Ci
Cnh n/m n/m 2n Cn' Uh a = Cn' b = Uh; an = E, 2n C lh = C,
2n 2n b 2 = E, ab = ba.
n+6
Dn n22 n22 2n Cn' nU a = Cn' b = U; an = E -- Dn""""'" Cnv
2
n+3
n2 n2 b2 = E, ba = an-lb. - -
2
n 2 2 n
Dnh ----- -- 4n Cn' nU, a = Cn' b = U, e = u h; n+6 Dnh = Dn x C,
mmm mmm
2nm2 2nm2 (J h' nav an = E, b2 = E, e 2 = E; n+3 D2ph = D2p X Ci
ba = an-Ib, ae = ea,
be = eb.
Dnd 2n2m 2n2m 4n S2n' nU, a = S2n' b = U; a 2n = E n+3 Dnd ...... D 2n
i'i2/m i'im nUd b2 = E, ba = a 2n - l b. D2p +l d = D2P + 1 X Ci
T 23 23 12 3C 2,4C 3 a = C 2zo b = C 31 ; a2 = E, 4
b3 = E, bab = ab 2a.
7d 43m 43m 24 4C 3 ,3S4 a = S;:, b = C 31 ; a4 = E, 5
6u b 3 = E, aba = b 2.
2_
T" -3 m3 24 3C 2,4S 6 a = C 2zo b = S61; a 2 = E, 8 T" = T X Ci
m
3u b6 = E, bab = ab 2a.
0 432 432 24 4C 3 ,3C4 a = C4zo b = C 31 ; a4 = E, 5

6U b 3 = E, aba = b 2.
4_2
Oh -3- m3m 48 4S 6,3C4 a = C4zo b = S61;a 4 = E, 10 Oh = 0 X Ci
m m
6U,3u b6 = E, ab 3 = b 3 a,
6u' ba 3 /j = a.
Y 532 532 60 6Cs ,10C3 , a = C S1 ' b = C31 ; as =E 5
15C2 b 3 =E, aba = b 2
Yh 2
53- 53m 120 6810 , a = C S1 ' b = S61; as = E, 10 Yh = YxCi
n 1086 , b 6 =E, ba4b = a,
15C2 ,150- ab 3 = b 3a
j = 1,2, ... ,t . (3.2.1)

The set of points
I qj = gjql (j= 1,2, ... ,t) (3.2.2)
forms an orbit of the point ql. The point qj of the orbit has a site symmetry
group
(3.2.3)
isomorphous to Gl (G;+-+Gl>j = 1,2, ... ,t).

Thus, an orbit may be characterized by a site group 0 1 (or any other
from the set of groups OJ). The number of points in an orbit is equal to the
index t = no/no I of the group 0 1 in O.
If the elements gj in (3.2.1) form a group P then the group G may be
factorized in the form G = PG l . The group P is called the permutation symme-
try group of an orbit with a site symmetry group G1 (or orbital group).
In a molecule all points of an orbit may be either occupied by atoms of the
same chemical element or vacant. Only the groups Cn' Cnv , Cs may be site
symmetry groups in molecules. A molecule with a symmetry group G may have
G (for the central atom), Cn' Cnv , or Cs groups as site symmetry subgroups.
For any point symmetry group a list of possible orbits (and corresponding
site groups) can be given. In this list some groups may be repeated more than
once. This occurs if in G there are several isomorphous site symmetry subgroups
differing from each other by the axes Cn(U) or the planes (1. All the atoms in a
molecule may be partitioned into orbits.
Example. The list of orbits in the group G = C4v is
(3.2.4)
The number of atoms in an orbit is given in brackets. In a molecule of the
type X Y4Z (Fig. 3.3) the atoms are distributed over three orbits: atoms X and Z
occupy positions on the main axis with site symmetry G" = G = C4v and four
atoms Y occupy one of the orbits with site symmetry group Cs The symmetry
information about this molecule may be given by the following formula:
A.=----+--- y
Fig.3.3. XY4 Z-type molecule and its sym-

X cry metry elements
3.3 Space Groups 43
which indicates both the full symmetry of the molecule (in front of the brackets)
and the distribution of atoms over orbits.
For molecules IFs and XeF4 0 (having the same symmetry C4v ) this formula
becomes
and (3.2.6)
As we can see, atoms of the same chemical element may occupy different orbits,
i.e., may be nonequivalent with regard to symmetry.
3.3 Space Groups
3.3.1 Symmetry of a Model of an Infinite Crystal.

Symmorphic and Nonsymmorphic Space Groups
In a crystalline solid, atoms are arranged in a regular periodic structure. The
periodicity of the crystalline structure means that it can be described by a
Bravais lattice. This lattice is a collection of mathematical points arranged
in such a way that each lattice point has the same environment in the same
orientation.
The complete similarity of the environment of each lattice point is possible
only in an infinite lattice. A real crystal cannot contain an infinite number of
atoms. However, the model of an infinite crystalline lattice will be a close ap-
proximation to a real crystal if one is interested in those properties which are
not influenced by the surface (electron density distribution inside the crystal,
optical excitations, etc.).
The three-dimensional Bravais lattice is defined by three basis translation
vectors a 1, a 2 , a 3 . Any lattice point is the end of one of the pure translation
vectors a. = n 1a 1 + n 2a Z + n 3a 3 (n1' n z , n3 are integers). A translation sub-
group T of the space group G consists of an infinite number of pure translations.
The parallelepiped constructed from the vectors a 1, a z , a 3 is called the
primitive (elementary, fundamental) unit cell. The infinite lattice as a whole is
made up of an infinite number of primitive unit cells. All primitive unit cells are
of equal volume v.. = (a 1 [a 2 x a 3]). The basis vectors a 1, a z , a3 can be chosen
in many different ways. We shall make the choice also made by Miller and Love
[3.2]. In addition to the symmetry of the pure translation group T, the Bravais
lattice is also invariant under point-group operations R forming a holo-
symmetric point group P of one of seven crystal systems (syngonies): C;(l)-
triclinic, Czh (2/m)-monoclinic, Dzh(mmm)-orthorhombic, D4h (4/mmm)-
tetragonal, D3 i3m)-trigonal, D6h (6/mmm)-hexagonal, Oh(m3m)-cubic.
Other point groups for point symmetry groups of the Bravais lattice are excluded
because (i) in an infinite lattice only 2-, 3-, 4- and 6-fold rotation axes are
possible; (ii) P must contain the space-inversion operation I since if a is a vector

of the Bravais lattice then so is -a; (iii) together with axes of orders 3,4 and 6
the point group P also contains reflection planes that pass through these axes.
The crystal systems CZh , DZh ' D4h , Oh may be obtained with Bravais lattices
of different types (primitive, base-, body- or face-centered). The unit cell vectors
may be chosen in such a way that the unit cell clearly exhibits the point symme-
try P of the lattice. This cell is called the conventional (crystallographic) unit cell
specified by the vectors a, b, c. In a centered (non-primitive) Bravais lattice the
conventional unit cell has n times larger volume than the primitive unit cell
(n = 2 for base- and body-centered lattices and n = 4 for a face-centered lattice).
Respectively, the crystallographic unit cell contains n lattice points while the
primitive unit cell, obviously, contains only one lattice point. The third possible
choice of the unit cell of a Bravais lattice is obtained by placing the coordinate
system origin 0 at anyone of the lattice points and drawing the planes that
perpendicularly bisect the lines joining 0 to the nearest (and sometimes to its
next-nearest) neighbors. The polyhedron bounded by these planes is called the
Wigner-Seitz unit cell. This unit cell has the same volume as the primitive cell,
contains only one lattice point and also exhibits the point symmetry of the
lattice, just as the crystallographic unit cell does. Figure 3.4 shows primitive,
crystallographic and Wigner-Seitz unit cells for the face-centered cubic lattice.
The point symmetry group F of a crystalline solid must be compatible with
the point symmetry P of the Bravais lattice of that solid. This means that F s; P,
i.e., the point group F of the crystal with the symmetry of space group G
coincides with the holosymmetric point group P or with one of its subgroups.
There are only 32 possible crystallographic point groups F (Sect. 3.2.1) or 32
crystalline classes.
A general operation of the space group G may be represented by the Seitz
symbol (Ril Vi + a.) with the meaning that Ri is an operator of the point group
F and ti. = Vi + a. is a translation vector to be associated with it. The symmetry
group G operator gi. = (R;lti.) acts on the points of the space (active operator):
(R;lti.)r = r' = Rir + Vi + a .
The elements of the pure translation group T are written in the form (Ela.).
The translation group T is an invariant subgroup of G since (RltHEla.HRltfl =
(EIRa.). Any operation R of the point group F is one of the point symmetry
operations of the Bravais lattice symmetry point group P, i.e., it transforms the
_ _ _ _ _ .J,
Fig. 3.4. Primitive, crystallographic and Wigner-Seitz unit cells for a face-centered cubic lattice
3.3 Space Groups 45
lattice vector all into the lattice vector a' = Rail' Thus (EIRa E T, which proves
ll )
the invariance of the subgroup T of the group G (T <J G).

It was shown by Fedorov and Schon flies that there are 230 space groups
(73 space groups are symmorphic, 157 space groups are nonsymmorphic).
In a symmorphic space group the operations of the point group F s::: P and
the operations of the translation group T are separable because the operations
of the point group F are symmetry operations of the crystal. Since T <J G the
symmorphic space group G is the semi-direct product of the translation group
T and point group F: G = T /\ F. The space group of a Bravais lattice is
evidently symmorphic and can be written as G = T /\ P.
For the 157 nonsymmorphic space groups the point operations Ri no
longer form a subgroup of G: by replacing some of the elements of F by screw-
axis rotations or glide-plane reflections one can no longer write G as a semi-
direct product of translation group T and point group F. However, from the
invariance of the translation group Tin G the existence of the factor group G/T
follows, formed by cosets in the decomposition
nF
G= I (R;lv;)T . (3.3.1)
i=l
The set Q of coset representatives (R;lv;) in (3.3.1) does not form a group so
that G = TQ is a conventional product.
The factor group G/T is isomorphic to the point group F (G/T +-+ F)
for both the symmorphic and nonsymmorphic space groups. For symmorphic
groups the representatives of the co sets in (3.3.1) may be chosen in such a way
that they form a point group F: (R;lO) E F. For nonsymmorphic space groups
one can set R1 = E and Vi (fractional translation associated with R i ) to be a
vector of least possible magnitude: the components vij (j = 1,2,3) of Vi with
respect to the basic translation vectors aj are assumed to satisfy the condition
0< vij < 1. The set Q of coset representatives in (3.3.1) depends on the choice of
the coordinate system origin but for nonsymmorphic space groups there must
be one or more non-zero Vi in (3.3.1).
To denote a space group both international and Schonflies symbols can be
used. As an example let us consider the international P42 /mnm and Schonflies
D!t symbols of the same symmetry group of the structure of rutile, Ti02 The
first (international) symbol consists of the lattice type symbol P (primitive or
simple) and three positions showing the symmetry directions [001], ([100],
[010]), ([110], [110]). The symbol 42/mnm has the following meaning: the first
position-4 2 /m-indicates that the main four-fold axis is directed along the
z-axis [001], which is a screw axis; orthogonal to this axis plane is the reflection
plane (Jz- The second position-n-indicates that the (Jx and (Jy planes are
glide planes passing through the y- and x-axes [010] and [100]. In the third
position-m-planes u xy , (JXY are reflection planes. This space group is non-
symmorphic as it contains rotations around a screw axis and reflections in glide

planes.
The Schonflies symbol DJ: of this group is less informative. It shows that
the crystallographic point group F (the crystal class to which this space group is
related) is D4h (4/mmm) but the upper subscript has to be used to find the correct
one of 20 space groups with the same crystal class D4h , e.g., in the International
Tables for Crystallography [3.3]. The decomposition (3.3.1) of the space group
DJ: for different choices of the origin will be considered in Sect. 3.4.2.
In this consideration the space group G was assumed to have infinite order,
because the translation group T for an infinite lattice consists of an infinite
number of pure translations. To apply the theory of finite groups to space
groups so-called periodic boundary conditions are imposed and, instead of a
model of an infinite crystal, a finite cyclic model is considered.
3.3.2 Symmetry of a Cyclic Model of a Crystal

To define a finite cyclic system, let us make a linear transformation of the
primitive lattice translation vectors ai'
L = Idetll ?: 1 , (3.3.2)
where the integer coefficients lij form the matrix 1. The transformation (3.3.2) for
L > 1 determines a large unit cell of the direct lattice. It may be chosen in
the form of a parallelepiped with vectors Aj as edges or in the form of the
corresponding Wigner-Seitz unit cell.
The particular form of the matrix 1in (3.3.2) defines both the large unit cell
volume (which is L times larger than that of a primitive unit cell) and the
symmetry of the direct lattice based on the group TA. of the translations
nj are arbitrary integers . (3.3.3)
The group TA. is an invariant subgroup of T,,<J G (translation group

of the infinite lattice with primitive vectors a;) so that the co sets (Ela(i)TA.
(i = 1,2, ... , L) in the decomposition
L
Til = L (Ela(i)TA
;=1
(3.3.4)
form the factor group Til/TA = T(A) of order L. So-called inner translations of
the large unit cell are assumed to be chosen as a(i) in (3.3.4).
A cyclic system CA) is defined as a large unit cell with identical opposite
faces, i.e., the cyclic boundary conditions are introduced for the large unit cell
3.3 Space Groups 47
itself. The translation symmetry of CIA) is characterized by a three-dimensional

cyclic group rIA) of order L with the elements (Ela(i from (3.3.4) and multipli-
cation law modulo TA. The group rIA) is isomorphic to the factor group T(A).
Let l(/I)(R) be the transformation matrix of the translation vectors a i under
the point symmetry operation REF:
Ra i = L lW(R)ai'
i'
(3.3.5)
The corresponding transformation matrix for the translation vectors Aj in (3,3.2)

IS
(3.3.6)
(3.3.7)
The operation (R'lv' + a.) EGis compatible with the translation symmetry of
the lattice composed of large unit cells, if the vectors R' Aj are integer linear
combinations of the vectors Aj , i.e., the matrix l(A)(R') is integer. All these
operations (R'lv' + a.) form a group G' c G. The rotations R' form a point
group F' c F of order nF' ~ nF As
(R'lv' + a.)(EIAJ(R'lv' + aar t = (EIR' AJ ' (3.3.8)
the translation group TA is an invariant subgroup of the group G'. The co sets in
the decomposition
L nF'
G' = L L (R~lv; + a(iTA (3.3.9)
i=l s=l
form the factor group G(A) = G'/TA of the order nF'L.

The coset representatives (R' Iv; + ali~ in (3.3.9) contain the inner transla-
tions ali) of the large unit cell (i = 1,2, ... , L) and rotational parts R' E F' forming
the point group F' of the space group G'.
Let us introduce a modified multiplication law modulo TA , which does not
distinguish between the translations of the group TA The set of nF'L elements
(R~lv; + ali~ forms a group CIA) (modulo TA ), which is the symmetry group of
the cyclic system CIA).
The group CIA) is isomorphic to the factor group G(A). Both groups (C(A)
and G(A are homomorphic images ofthe space group G'. The translation group
TA is the kernel of this homomorphism.
If the space group G' coincides with the space group G the transformation
(3.3.2) is called symmetric. In this case the point symmetry of a cyclic system
coincides with that of an infinite crystal. The symmetric transformation (3.3.2)
retains the point symmetry of the Bravais lattice, but it is compatible with a
change of its type in the framework of the same crystalline system. The non-
symmetric transformation (3.3.2) leads to a cyclic system with the point symme-
try group F' which is lower than that of an infinite crystal.
The smallest possible cyclic system Ca) is a primitive unit cell with the
symmetry group c(a) of the order nF (F(a) _ F). The so-called main region
of a crystal usually introduced in solid state theory is also a cyclic system
corresponding to the transformation (3.3.2) with very large L = Nl N2N3: it is
assumed that there are Ni primitive unit cells in direction a i (i = 1,2,3) (where Ni
is a very large number). When the cyclic boundary conditions are introduced for
the main region of a crystal, the translation group TA consists of translations
Ai = Niai (i = 1,2,3), i.e., the transformation matrix I in (3.3.2) is assumed to be
diagonal. Usually no attention is paid to the fact that the main region possesses
the point symmetry of an infinite crystal only if the corresponding transforma-
tion (3.3.2) is symmetric. For example, the main region for a cubic crystal may
be defined with Nl = N2 = N 3 The space group G of the infinite crystal may
be obtained as a limit of the symmetry groups of a sequence of increasing
cyclic systems.
3.4 Site Symmetry in Space Groups
3.4.1 Crystallographic Orbits. Wyckoff Positions

To characterize a space group G an analytical description may be employed,
which states for a space group the coordinates of all points that are equivalent
to a chosen point q with coordinates (xyz). Analytical description of all 230
space groups is given in the International Tables for Crystalography [3.3] and is
based on the fact that for a given space group G all points of a three-dimensional
space are subdivided into sets of symmetrically equivalent points called crystal-
lographic orbits.
All the points of a given crystallographic orbit may be obtained from one
(arbitrary) crystallographic orbit point q (generating point) by applying to the
latter all the operations of space group G. Due to the infinite number of transla-
tions there is an infinite number of points in each space group crystallographic
orbit. Anyone of the crystallographic orbit points may represent the whole
crystallographic orbit, i.e., may be a generating point q of the crystallographic
orbit.
All symmetry operations (Ril Vi + a.), i = 1,2, ... , n, of a space group G that
satisfy the condition (Rdvi + a.)q = q form a finite site symmetry group (G,) of
q with respect to G. The site group G, is isomorphous to one of the 32 crystal-
lographic point groups. If the origin of the space group is at the position q the
elements of the site symmetry group G, will be of the form (R 10).
The site symmetry groups Gj of different points qj of the same crystallo-
graphic orbit are conjugate groups of G 1 = Gq , i.e., the site symmetry group
3.4 Site Symmetry in Space Groups 49
G j and Gj of points qj = q and qj of the same orbit are related by gjGjgj- j =

Gj (gjEG, gj$Gjo gj$Gj , gjqj = q). For a point q at a general position the
site symmetry group G q consists of only the identity operation (EI 0); the site
symmetry group of a point at a special position includes at least one other sym-
metry operation in addition to the identity operation.
An infinite number of crystallographic orbits for a given space group G can
be subdivided into sets of so-called Wyckoff positions of G. All the crystallo-
graphic orbits which have the same (not only isomorphic but the same) site
symmetry group belong to the same Wyckoff position. If the coordinates of the
generating point of a crystallographic orbit do not contain variable parameters
the corresponding Wyckoff position consists of only one crystallographic orbit;
in other cases an infinite number of crystallographic orbits belongs to the same
Wyckoff position with variable parameters.
The different Wyckoff positions are labeled by small Roman letters. The
maximum number of different Wyckoff positions of a space group is 27 (in the
group Dih = Pmmm).
The various possible sets of Wyckoff positions for all the space groups
Table 3.2. Wyckoff positions and oriented site symmetry groups for the
space group D!:
q Coordinates of the Wyckoff positions in the unit cell
2a m.mm (0,0,0), (M, t);

2b m.mm (0,0, t), (t, t, 0);
4c 21m .. (0, t, 0), (O,M), (t,o,t), (t, 0, 0);
4d 4 .. (0, H), (0, H), (t,o,~), (t.o,i);
4e 2.mm (0, 0, z), (M,z + t), (t.M - z), (0,0, -z);
4f m.2m (x, x, 0), (-x, -x,O), (t - x,t + x,t), (t + xo! - x,t);
4g m.2m (x, -X,O), (-X,X,O), (t + x,t + x,t), (t - x,t - x,t);
8h 2 .. (O,t,z);
8i m .. (x,y,O);
8j .. m (x,X,z);
16k (x,y,Z), (-x, -y,z),
(EIO) (C 2z IO)
(t - y,t + x,t + z), (t + y,t - x,t + z),
(C 4z lv) (C;~lv)
(t - x,t + Yo! - z), (t + x,t - y,t - z),
(Uylv) (Uxlv)
(y,x, -z), (- y, -x, -Z),
(UxyIO) (Ui'yIO)
(-x, - y, -Z), (x,y, -z),
(110) (O'zIO)
(t + y,t - x,t - z), (t - yo! + x,t - z),
(S4zlv) (S;:lv)
(t + x,t - y,t + z), (t - xo! + y,t + z),
(O'ylv) (ax Iv)
(- y, -X,Z), (y,x,Z).
(O'xyIO) (O'xyIO)
are given in the International Tables for Crystallography [3.3]. As an example,

Table 3.2 lists those for the space group DI: (P4 2 /m2tfn2/m). For this group
there are 11 different Wyckoff positions denoted by letters from a to k. The
number of crystallographic orbit points in the primitive unit cell equals nF/n lJ ,
where nF = 16 is the order of the point group D4h and n, is the order of the site
symmetry group GIJ. Only generating points are given in the table for the orbits
of special positions h to j. The number of points in a Wyckoff position and their
coordinates are given in the International Tables with respect to the conven-
tional unit cell of the lattice (for the space group Dl: with a simple Bravais
lattice, the conventional unit cell coincides with the primitive unit cell). All the
crystallographic orbit points in the unit cell are given in Table 3.2 for a point k
of general Wyckoff position (xyz). This information allows one to determine the
appropriate Seitz space group symbols for the coset representatives in the de-
composition (3.3.1) of space group G with respect to the translation group T. In
Table 3.2 these symbols are written under the coordinates of the points obtained
from the point r(x, y, z) by performing the space group operation (R Iv). The
orientation of the symmetry elements with respect to the tetragonal lattice trans-
lation vectors at (a, 0, 0), a 2 (0, a, 0) and a 3 (0, 0, c) is shown in Fig. 3.5. In the
point group D4h there are four rotations around two-fold axes (Ux , Uy , UXY ' UXY )
and four rotations (including the identity operation) around the main four-fold
Z-axis (E, C4z , Cl z = C 2z , clz = Ci;)
The remaining 8 symmetry operations are all products of inversion J with
rotations: J; reflections (JX' (Jy, (Jxy, (Jxy, (Jz in the planes perpendicular to the
corresponding two-fold axes and Z-axis; mirror rotations Sizt. S4z' It is seen
from Table 3.2 that the elements of the point group D2h (E, C2z , UXY ' Uxy ,/, (Jz'
(Jxy' (J.xy) appear in the co sets decomposition (3.3.1) without fractional transla-
tions. These elements form the site symmetry group of the coordinate system
origin placed at the point of Wyckhoff position a(O, 0, 0). The second point of
this position (112, 112, 112) is obtained from the first one by application of any
symmetry operation from these eight (C4z ' C izt. S4z' S izl , Ux , Uy, (Jx' (Jy), which
come into the coset representatives in (3.3.1) with fractional translation v =
UXy crxy
Uy crx
--------~~---------
a2
Fig. 3.5. Orientation of the symmetry elements with

respect to the tetragonal lattice translation vectors for
the space group D!:
(112, 112, 112). We therefore write the space group D!i, (for the case when the
Wyckoff position a is taken as the origin) as
Dlt= I
ReD 2h
[(RIO)T+(UxI1/2,1/2,1/2)(RI0)T] (3.4.1)
Considering the full international symbol of the space group Dlt,

P4 2/m2tfn2/m, we see that the coset representatives in the decomposition of
Dlt with respect to the translation group T correspond to this symbol. Indeed
in our example of a tetragonal lattice the three positions in this symbol corre-
spond to the symmetry directions [001]; [100], [010]; and [110], [110];
respectively. Rotation through the angle n/2 about the Z-axis is followed by
translation along this axis by one-half of the translation vector a 3 , as is seen
from the symbol for the element (C4z I1/2, 1/2, 1/2). The notations 21 and 2 for
two-fold x- and xy-rotation axes agree with the Seitz symbols (UxI1/2, 1/2, 1/2)
and (UxyIO, 0, 0). Finally, the notations m, n, m for the reflection planes perpendi-
cular to the corresponding symmetry directions in the international symbol for
the space group agree with the Seitz symbols (O"zIO, 0, 0), (O"xI1/2, 1/2, 1/2) and
(O"xyIO, 0, 0), respectively. The space group Dlt may also be described by its six
generators: three primitive translations (ElaJ, (i = 1,2,3) of the simple tetra-
gonallattice and three generating elements (C4z I1/2, 1/2, 1/2), (UxI1/2, 1/2, 1/2),
(110,0,0).
The coordinates of Wyckoff positions a, b, c, d do not contain free parame-
ters (Table 3.2); those of e, j, g, h positions contain one free parameter; the
coordinates ofthe positions i andj contain two free parameters. This means that
an infinite number of Wyckoff sets e-jexists in the crystal but the sets a, b, c, d
consist of only one crystallographic orbIt. Pairs of Wyckoff positions a-b, j-g,
and i-j have isomorphic site symmetry groups (D2h' C2v and Cs respectively).
3.4.2 Oriented Site Symmetry Groups. Choice of Origin

The difference between oriented site symmetry groups of different Wyckoff
positions is due to different orientations of the elements of the site symmetry
group GIJ with respect to the lattice. The difference arises when similar symmetry
elements (reflections in planes and rotations about two-fold axes of symmetry)
occur in more than one class of elements of the point group F.
Only eleven site groups [C2(2), Cs(m), C2h (2/m), C2v (2mm), C3v (3mm),
D2(222), D 3(322), D2d (42m), D 3l32m), D2h (mmm), and D3h(62m)] can have
different orientations with respect to the Bravais lattice. Oriented site symmetry
symbols show how the symmetry elements at a site are related to the symmetry
elements of a space group. The site symmetry symbols display the same
sequence of symmetry directions as the space group international symbol. Sets
of equivalent symmetry directions that do not contribute any element to the site
symmetry group GIJ are represented by a dot. In our example of the space group
Dl: the site symmetry groups Ga , Gb do not contain reflection in the planes
(the dot is at the second position) and the site group Ge = 2.mm does not
(Jx, (Jy
contain reflection in the plane (Jz (a dot is at the first position, Table 3.2).
The fractional translations Vj of the representatives of co sets (Rjlv) in the
decomposition (3.3.1) and the coordinates of the Wyckoff position depend on
the choice of origin (with respect to which the space group elements are written)
and on the labeling of axes (choice of setting) [3.4, 5].
Let (Rolv) be some coset representative written with respect to the origin 0
and RoY = y'. The form of the Seitz symbol (Rolv) is affected by displacing the
origin of the coordinate system by a vector d from point 0 to point 0 ' [see
(3.1.43) in Sect 3.1.5, Fig. 3.2]
By definition, the symmorphic space groups contain, together with each
element (Ria), the elements (RIO) and (Ela) of the point group F and translation
group T, respectively. This means that for a symmorphic space group the origin
o may be chosen in such a way that the site symmetry group of 0 is the point
group of the crystal F. Therefore all the fractional translations v in the Seitz
symbols of the coset representatives (R Iv) are zero. Such a choice of origin is
accepted for symmorphic space groups in the International Tables.
For nonsymmorphic space groups, all the Wyckoff positions have point site
symmetry groups F" c F so that some fractional translations will be nonzero
for any choice of origin. In this case different origins are used by different
authors.
For example, the space group Dl: is described in [3.2, 6, 7] for origins at
Wyckoff positions c, eand d, respectively. Instead of the decomposition given
in (3.4.1) we have for these origins the following decompositions of the space
group Dl::
(e) Dl: = L [(RIO)T + (Ux I1/2, 1/2, O)(R I0) T

ReC 2v
+ (110,0, 1/2)(RIO)T + (C4z I1/2, 1/2, 1/2)(RIO)T] (3.4.2)
(d) Dl: = L [(RIO)T + (Ux I1/2, 1/2,0)(RI0)T

RES.
+ (110,0, 1/2)(RIO)T + (Uxy I1/2, 1/2, O)(R I0) T] (3.4.3)
(c) Dl: = L [(RIO)T + (Ux I1/2, 1/2, 1/2)(RI0)T

REC 2h
+ (Ux yI1/2, 1/2,0)(RI0)T + (C4z IO,0, 1/2)(RI0)T] (3.4.4)

Table 3.3. Fractional translations of generators of space group D!:

for different choices of origin
Origin at q [Ref.] Fractional translations "i

C4 % Ux I
a [3.3] (1/2,1/2,1/2) (1/2,1/2,1/2) (0,0,0)

c [3.2] (0,0,1/2) (1/2,1/2,1/2) (0,0,0)
(EIO,l,O) (EII,O,O) (EII,O, 0)
d [3.7] (0,0,1/2) (1/2, 1/2,0) (0,0,1/2)
(EIO,1,O) (EIO, I, 1)
e [3.6] (1/2,1/2,1/2) (1/2,1/2,0) (0,0,1/2)
(EIO,O,l)
For the coordinates of Wyckoff positions:

a (0,0,0), c (112,0,0), d (0,112,114), e (0,0, -114)
The coset representatives in (3.4.2-4) are chosen in such a way that each compo-
nent vji of the fractional translation Vj is a positive real number in the range
0< vji < 1.
The fractional translations associated with generators of a point group F
contain all the information about the choice of the origin. For the space group
Dl: this information is given in Table 3.3. However, it may be shown that these
four descriptions of the space group Dl: do not use the same coset representa-
tives in the corresponding group decompositions. Using (3.1.43) it is easy to find
that the one-to-one correspondence of the coset representatives is restored if
some pure translations are added to the generating elements (the pure transla-
tions are given in Table 3.3 for those elements for which they are nonzero).
For example, let us consider the correspondence between coset representa-
tives (laIO, 0, 0) and (lei 0, 0, 0). Using (3.1.43) for d = re - ra = ad2 we obtain
(laIO, 0, 0) = ((Ilad - d) = (lel-al) = (EI-al)(leIO,O,O), where la, Ie mean the
inversion at Wyckoff positions a and c, respectively. This means that by
displacing the origin from a to c and maintaining the choice of coset representa-
tives one has to take (lel- ad as the generating space group element, instead of
(laIO, 0,0). We return to this question in Sect. 3.8.5 in a discussion of the labeling
of irreps for the space groups.
The pure translations may appear in the Seitz notations of the site
symmetry group G9 c G elements when the coordinate system origin is not
at q. For example, the site symmetry group Gb = D2h isomorphic with Ga
contains pure translations in Seitz notations of some elements. For instance,
(UxyIO, 0, 0)(1/2,1/2,0) = (-1/2, -1/2,0) = (1/2,1/2,0) - a l - a2' Therefore the
b site symmetry group element will be (UXyla l + a 2) when the origin is placed at
Wyckoff position a.
The elements of the site symmetry group Gb (when the origin is at a) are
the following: (EIO, 0, 0), (C2z la 1 + a 2), (UxyIO), (UXyla l + a 2), (lla l + a 2), (CTzIO),
(CTxyla l + a 2), (CTxyIO). We take this into account in Sect. 4.2 when generating the
induced representations of space groups.
3.4.3 Crystal Structure Types. Crystals with Space Group DU

The crystal structure type is specified when one states which atoms occupy which
sets of Wyckoff positions for the corresponding space group. To distinguish
different structures of the same type one needs the numerical values of lattice
parameters and additional data if Wyckoff positions with free parameters in
coordinates are occupied. When describing the crystal structure type one also
gives the value of Z (the number of formula units in the conventional unit cell).
This information is, in principle, not necessary as Z is defined by the chemical
formula of the compound and the degeneracy occupied by atoms Wyckoff
positions in the unit cell. It is also necessary to take into account that the
primitive unit cell of any crystal contains half the number of atoms in a body-
centered cell, one-quarter the number in a face-centered, and half the number
in an A, B, or C-face-centered cell. Rhombohedral cells contain one-third the
number of atoms in the corresponding hexagonal cell.
The Wyckoff site description of a crystal structure type is also origin depen-
dent. It was shown that equivalent alternatives often arise if two or more sets of
sites are physically equivalent [3.8]. The equivalent sites have the same point
group symmetry and the same orientations of symmetry elements with respect
to the lattice. For example, in the group DJ: these conditions are satisfied for the
pairs of positions a-b and f-g (Table 3.4). Correlations of equivalent Wyckoff
site descriptions for all the space groups are found in [3.8].
Now we consider different crystal structures with the same space group DJ:.
In Table 3.4 all the symmetry information about these structures is given: the
Table 3.4. Crystal structures with the space group D!t

Type of structure Occupation of Equivalent
formula unit. number Wyckoff positions Wyckoff site
of units Z by atoms description
Rutile Ti0 2 , Z = 2 2a Ti (a,J), (b, g)

4fO
Trirutile TiLi 2 F 6 , Z = 2 2a Ti (a, e,j,J), (b, e,j, g)
4e Li
8j F
4fF
4d Hf (d,J, g,j), (d, g,J,j)
4fHf
4g Hf
8j Al
NbOCI 3 ,Z = 4 4fNb (J, g, g, i), (g,J,J, i)
4g0
4g CI
8i CI
2a Pt (a,J,j), (b, g,j)
4f (NH 3)
8j CI
3.5 Symmetry Operations in Quantum Mechanics 55
number of formula units in the primitive unit cell, and the occupation of
Wyckoff positions by atoms. In the last column we give possible equivalent
Wyckoff site descriptions of the same structure. For example, the trirutile struc-
ture may be described by two equivalent sets of Wyckoff positions occupied by
atoms: 2a(Ti) 4e(Li) 8j(F) 4f(F) or 2b(Ti) 4e(Li) 8j(F) 4g(F). In the first descrip-
tion the origin of the coordinate system is chosen to be at the titanium atom, in
the second, the origin a is not occupied by an atom at all. In both equivalent
descriptions the description of the space group Dl: is assumed to be that given
in Table 3.2 (with the origin at Wyckoff position a).
This possibility of different equivalent descriptions of the crystal structure
types has to be taken into account when the symmetry of electron and phonon
states in crystals is analyzed. For analyses based on information about crystal
structure, it is necessary to use irreducible representations of the space group. A
descriptive account of these irreps is given in Sect. 3.8.
3.5 Symmetry Operations in Quantum Mechanics
3.5.1 Symmetry Group of a Quantum Mechanical System

The wave functions of quantum mechanical stationary states satisfy the time-
independent Schrodinger equation
H(r)t/J(r) = Et/J(r) . (3.5.1)

For the sake of simplicity we shall consider a one particle system, where the
wave function t/J(r) depends on the coordinates of only one particle, H(r) is a one
particle Hamiltonian operator and E the energy of the eigenstate t/J(r). Under
the operation g of the space as a whole, a point g-lr with the value t/J(g-lr) of the
wave function takes a new position r. The wave function t/J(r) with respect to the
fixed coordinate system is transformed under the operation g into the function
tfi(r) = t/J(g-l r). After this transformation the Schrodinger equation becomes
(3.5.2)
The transformation g is said to be a symmetry operation of the Hamil-

tonian H if H(g-lr) = H(r), i.e., if H is invariant under g. Euclidean operations g
that leave H invariant form a group. This group is called the symmetry group
of the Hamiltonian H or of the Schrodinger equation (3.5.1).
We introduce in the linear vector space L of functions t/J(r) the operators
(j = D(g) as
I D(g)t/J(r) = gt/J(r) = t/J(g-l r) . I (3.5.3)
The operators g are linear and the correspondence g -+ g is preserved in the

composition law:
(3.5.4)
Hence the set of operators D(g) = g (g E G) is a rep of G and L is the space of

this rep. If 9 EGis a symmetry operation of the Hamiltonian operator H then
Hgt/!(r) = H(r)t/!(g-l r) = Et/!(g-l r) = gEt/!(r)

= gHt/!(r) . (3.5.5)
This relation holds for any eigenfunction of H and for all linear combinations of
the eigenfunctions, i.e., for any function in the linear vector space L. Therefore
the following operator relation may be written:
D(g)H = HD(g) , gE G . (3.5.6)
It expresses in mathematical form the symmetry properties of the Hamiltonian

of a quantum mechanical system.
3.5.2 Wigner's Theorem

We choose in the space L a symmetry-adapted basis cp\~(r), where the index
i = 1, 2, ... , na labels the basis functions of the irrep r.t and the index I.l
distinguishes independent basis functions of equivalent irreps. The matrices of
the operators D(g) have in this basis a quasi-diagonal structure
(3.5.7)
We write the operator relation (3.5.6) in the chosen basis using the quasi-
diagonal form (3.5.7) of matrices D(g)
(3.5.8)
or
(3.5.9)
where the notation H allpv is introduced for matrices with matrix elements
(Hallpv)u' = Hialli,PV'
In accordance with Schur's lemmas (Sect. 2.2)
for fJ = r.t (3.5.10a)
and
for fJ =F r.t , (3.5.l0b)

3.5 Symmetry Operations in Quantum Mechanics 57
where E is an na x na unit matrix. Hence, in the symmetry-adapted basis the

matrix H of the Hamiltonian has quasi-diagonal structure (Wigner's theorem)
(3.5.11)
The block H(a) is composed of matrix elements
(3.5.12)
does not depend on the index i = 1, 2, ... , na and is repeated na times in the
matrix H of the Hamiltonian Ii.
In the symmetry-adapted basis the diagonalization of the matrix H is re-
duced to the diagonalization of its diagonal blocks. Every eigenvalue of the
matrix H(a) is repeated na times in the total list of the eigenvalues of the operator
Ii. From the above discussion it also follows that the eigenfunctions of the
Hamiltonian fl corresponding to the same eigenvalue are the basis functions of
an irrep of the symmetry group G of fl (in the absence of accidental degeneracy)
and the degeneracies of eigenvalues are equal to dimensions of the irreps of G
(also in the absence of accidental degeneracy). Thus the eigenstates I/I(r) and
their eigenvalues may be labeled by the irreps of the symmetry group G of the
Hamiltonian fl.
To obtain an approximate solution of the Schrodinger equation (3.5.1) for
molecules and crystals, often a function space of finite dimension is used. For a
large number of basis functions the diagonalization of the matrix H becomes
difficult, time-consuming work. But in a symmetry-adapted basis the matrix H
has a quasi-diagonal structure with na identical blocks H(a) related to an irrep a
of the symmetry group G of the Hamiltonian fl. It is obvious that for every irrep
a it is sufficient to diagonalize only one block H(a). So finding eigenvalues of the
operator fl becomes a simpler problem.
3.5.3 Time-Reversal Symmetry

Let the Hamiltonian operator H be real. The transition in the time-dependent
Schrodinger equation to a complex-conjugate equation with simultaneous
time-inversion substitution t-+ - t
.Jo..cJt/f(r, t) = H~ .1,( ) iii al/l*(r, - t) = fll/l*(r - t) (3.5.13)

1ft at 'I' r, t ,
at '
shows that the functions I/I(r, t) and I/I*(r, - t) are solutions of the same time-
dependent Schrodinger equation. This combined operation (complex conju-
gation + time inversion) is called the time-reversal transformation. Applying
this operation to the time-independent Schrodinger equation for the time-
independent part of stationary state wave functions
filjl(r) = EIjI(r) , filjl*(r) = EIjI*(r) , (3.5.14)
we see that ljI(r) and 1jI*(r) are the eigenfunctions of the same real operator fi
belonging to the same eigenvalue E. So with respect to the time-independent
part of stationary states ljI(r) the time-reversal operator reduces to a simple
complex conjugation,
1 KIjI(r) = 1jI*(r) 1 (3.5.15)
Let ljIi (i = 1,2, ... , n) be eigenfunctions of a real Hamiltonian fi belonging

to an eigenvalue E and also be the basis of a unitary irrep D(g) with a character
X(g) of its symmetry group G (g E G):
or gljl = IjID(g) , (3.5.16)
where IjI is a row offunctions ljIi' The functions Kljli = ljIi* are also eigenfunctions
of fi belonging to the same eigenvalue E, but transforming according to the
irrep D*(g) with a character X*(g) of G. In fact,
(3.5.17)
or
1 g(KIjI) = (KIjI)D*(g) (3.5.18)
The irreps D(g) and D*(g) may be either equivalent or inequivalent. The
functions ljIi and Kljli may be linearly dependent or linearly independent. There
are three cases:
1) The functions ljIi and Kljli are linearly dependent and are bases of equivalent
irreps [X(g) = X*(g)];
2) The functions ljIi and Kljli are linearly independent and transform according
to inequivalent irreps [X(g) of. X*(g)];
3) The functions ljIi and Kljli are linearly independent and are bases of equiva-
lent irreps [X(g) = X*(g)];
In cases 2 and 3 the eigenvalue E belongs to 2n states ljIi and Kljli' They form
a basis of the rep of the group G which is the sum of two irreps D(g) and D*(g)
of the same dimension n. Thus the degeneracy of the eigenvalue E doubles with
respect to that caused by the symmetry group in the space. In case 1 there is no
additional degeneracy. However, linear dependence of the functions ljIi and Kljli
may be explained by an additional symmetry beyond that described by the
elements of the group G. The linear independence of the functions ljIi and Kljli in
3.6 Irreducible Representations of Rotation and Full Orthogonal Groups 59
case 2 follows from the inequivalency of the irreps D(g) and D*(g) according to
which they transform.
In tables of irreps of a group G the complex conjugate irreps are usually
united in one so-called physically irreducible rep. In cases 1 and 3 the irreps D(g)
and D*(g) are equivalent:
D(g) = AD*(g)A -1 , AA+ =E . (3.5.19)
If the functions", transform according to an irrep D(g) then the functions

ljJ = ",A (and the functions If", also) transform according to the irrep D*(g):
90 = 9",A = ",DA = ",AA- DA = 0D*(g)

1 . (3.5.20)
The functions transforming according to the same rep (with the same matrices)
are either proportional to each other or linearly independent. Suppose that the
functions ",A and R", are linearly dependent,
(3.5.21)
Since the functions are supposed to be normalized, then 1212 = 1. In the case
of a real rep the matrix A is symmetric [AA* = E; (2.2.47)], otherwise anti-
symmetric [AA* = -E; (2.2.48)]. We apply to both parts of(3.5.21) the opera-
tion R
(3.5.22)
Substituting If", according to (3.5.21) and using the property of the matrix A
(AA * = E), we get from (3.5.22)
(3.5.23)
If the irrep D(g) is not real then the obtained contradiction ('" = - "')
proves that the initial supposition (3.5.21) is erroneous and the functions R",
and", A (or otherwise R", and",) are linearly independent. The reality of the rep
D(g) is compatible with the linear dependence of the functions If", and ",A (or
If", and "') although they may be linearly independent.
If the functions If", and", are linearly independent eigenfunctions of some
real Hamiltonian belonging to the same eigenvalue and forming the basis of a
real rep then this additional degeneracy is classified as accidental. It is not
affected by either the space symmetry group G or time-reversal symmetry.
3.6 Irreducible Representations of Rotation

and Full Orthogonal Groups
We shall give in this section some important results concerning the irreps of the
rotation group. Every rep of a finite group is equivalent to a unitary one. This
statement is valid for irreps of the rotation group as well, although it is continu-
ous. Therefore we shall deal only with unitary reps of the rotation group. Its
irreps are numbered by the indexj, which is related to the irrep dimension n by
n = 2j + 1. Thus the index j takes integral and half-integral values j = 0, 1/2, 1,
3/2, .... There exists only one irrep D(j) of every dimension n = 1,2, ....
For a special choice of basis (the so-called canonical basis) the matrix
elements of the irrep D(j) are
DW
1m
= L
k
J(j + m)!(j- m)!(j - 1)!(j + I)!
k!(j + 1 - k)!(j - m - k)!(m + k - I)!
k ~ 0, k :::;; j + 1, k :::;; j - m, k ~ 1- m , (3.6.1)
where a and b are Cayley-Klein rotational parameters describing the rotation p

(or t/J, 9, cp) according to (3.1.12, 13). The character of the irrep D(j) for the
rotation through an angle [3 about an arbitrary axis (such rotations are mem-
bers of the same conjugacy class) is equal to
x(j)([3) = sin[(j + 1/2)[3] (3.6.2)

sin ([3/2)
The rotations through [3 and [3 + 2n correspond to the same element of the

rotation group since the rotation by the angle 2n is a unit element of the group.
However,
(3.6.3)
For half-integral j the characters X(j)([3) and, as may be checked, the ma-
trices D(j) themselves change sign on adding the angle 2n to [3. This means that
in the irreps with half-integralj every rotation is mapped by two operators (two
matrices) differing in sign from one another. Such reps are called double-valued.
The matrices of the irrep withj = 1/2 in the canonical basis are equal to
(1/2)
Db
- a'
= (a b) (3.6.4)
These 2 x 2 matrices for arbitrary a and b satisfying the condition (3.1.13) form
the group denoted by SU(2). The rotation group 0+(3) and the group of
matrices SU(2) are connected by a simple relation: SU(2) -+ 0+(3) is a group
homomorphism. The kernel of the homomorphism is the group H of second
order with elements E and - E: SU(2)/H +-+ 0+(3). All the irreps D(j) (with inte-
gral and half-integralj) are ordinary (single-valued) irreps of the group SU(2).
3.6 Irreducible Representations of Rotation and Full Orthogonal Groups 61
The matrices (3.6.4) of SU(2) may be formally obtained if the parameters

f3x, f3y, f3z are assumed to change in the limits 0 ~ f3 < 2n, f3 = (f3; + f3; + f3;)1/2
[compare with (3.1.14)]. Thus the group SU(2) is isomorphous with the
"extended" rotation group 0+(3). In the latter the rotations through the angles
f3 and f3 + 2n are considered to be different. The rotation E through the angle
2n about any axis in the group 0+(3) is mapped by the matrix - E in the group
SU (2). The rotation E commutes with any other rotation since its image - E
(multiple of the unit matrix) commutes with any other matrix in the group
SU(2). The elements E and E form in 0+(3) an invariant subgroup H isomor-
phous to H in SU(2). The connection between the groups 0+(3) and 0+(3) is
the same as between the groups 0+(3) and SU(2). Every rotation g E 0+(3) is
mapped by two rotations g and g = gE in 0+(3). The group 0+(3) may be called
a double group with respect to the rotation group 0+(3). All the irreps DU) are
single-valued irreps of the group 0+(3). The irreps D(j) with half-integral j are
faithful irreps of 0+(3), i.e., different elements from 0+(3) are related to different
matrices of DU). The irreps D(j) with integralj are not faithful for the group 0+(3)
as two rotations (through f3 and f3 + 2n about the same axis) are mapped onto
the same matrix in the irrep DU).
The values transforming according to the irrep DU) are called the spinors
of rank j. Spinors of rank j = 1/2 are simply called spinors. A spin function
describing the states of internal angular momentum of an electron (or other
particle with spin 1/2) is a spinor. Wave functions of the orbital angular momen-
tum transform according to the irreps of the rotation group 0+(3) with integral
j. Therefore the reps of the rotation group with both integral and half-integral j
are widely used in quantum mechanics.
The products of spin and orbital angular momentum wave functions trans-
form according to the product of the corresponding reps. Linear combinations
of such products describe the states of a system with given values of the total
angular momentum. The direct product DU) x DU') is, in general, a reducible
rep. Its decomposition into irreps is
L
j+j'
D(j) x D(j') = D(i) (3.6.5)
i=lj-j'I
Let a system consist of two subsystems with definite values of the angular
momentum characterized by the numbers j and j'. Equation (3.6.5) shows that
the square of the total angular momentum may take on the values h 2 i(i + 1)
where i = (j + j'), (j + j' - 1), ... , Ij - /I.
The irreps of the full orthogonal group are easily deduced since it is a direct
product of the rotation group 0+(3) and the inversion group Ci : 0(3) =
0+(3) x Ci . The inversion group Ci has two one-dimensional irreps: ag (l, 1) and
au(l, -1). The irreps of 0(3) are obtained by multiplication of the irreps of
0+(3) by the irreps of Ci . Every irrep D(j) of 0+(3) with integralj generates two
irreps of 0(3):
D~j)(g) = D~j)(Ig) = DU)(g) , g E 0+(3) ;

(3.6.6)
D~j)(g) = -D~j)(/g) = DUl(g) , gE 0+(3)
An ordinary (polar) vector (e.g., the radius vector r with components x, y, z)

transforms according to the irrep D~l) of 0(3). The irrep D~l) determines the
transformation properties of a pseudovector or an axial vector (e.g., vector
product of two polar vectors).
Every double-valued irrep DU) (with half-integralj) of 0+(3) generates one
double-valued irrep of 0(3) in which anyone of the elements g, /g E 0(3) is
mapped by two matrices DU)(g).
3.7 Representations of Point Groups

In this section the irreps of point groups are briefly considered (see also
[3.9-11]).
Table 3.5 shows the relation between the 32 crystallographic point groups.
From this table it can be seen that the irreps of only the 11 proper point groups
(i.e., those consisting of pure rotations) may be used to generate the irreps of
all other crystallographic point groups. This generation is made by using the
isomorphism of groups or their structure in the form of direct products with the
inversion group C;. Hence, the information about the characters of the irreps of
all the 32 crystallographic point groups may be given in 11 subtables as in Table
3.6. These tables have the following format. The characters of isomorphous
groups are given in the same table. The labels of irreps are in the column under
the group symbol (according to Schonflies). The representative elements of the
conjugacy class are in the corresponding rows. The number before the symbol
of a class representative gives the number of elements in the class (its order). The
characters themselves are in the rows containing the labels of irreps. The follow-
ing letters are used for the notation of irreps: a and b for one-dimensional, e for
Table 3.5. Relations between crystallographic point groups
Proper point C1 C2 C3 C4 C6 D2 D3 D4 D6 T 0
group G
Groups isomorphous Ci S4 C 3h C2v C 3v C4v C6v 1d

toG C, S6 C 2h Dld D3h
D3d
GX Ci Ci C 2h S6 C4h C6h D2h D3d D4h D6h T" Oh
Gx C, C, C 2h C 3h C4h C6h D2h D3h D4h D6h
G 1\ C2 D3 D4 D6
G 1\ C; C 3v C4v C 6v Dld
D2 = C2 X C~, C 2v = C2 xC;, T = D2 1\ C3 , 0 = D2 1\ D3
Table 3.6. Irreducible representation characters of 24 crystallographic point groups and groups C s C s v and Y
Ci E I C 2h E C 2z I UZ C3 E C 3z C-'
3z
C2 E C 2z C 2v E C 2z uy Ux
~a 1 C, E UZ D2 E C 2z C 2y C 2x a
e(1} w w2
ag a a' ag a, a e(2) w2 w
au b a" -1 au a2 b, 1 -1 -1
w = exp(2ni/3)
bg b, b2 -1 -1
bu b2 b3 -1 -1
C4 E C 4z C 2z C-'
4z C6 E C 6z C 3z C 2z C-'
3z
C-'
6z
S4 E S4z C 2z S-'
4z C 3i E S6z C 3z I C-'
3z
S-'
6z
C 3h E S-'
3z C 3z UZ C-'
3z S3z
a a
b b -1 -1 a ag a' 1
e(1} e(1) -1 -i b au a" -1 -1 -1
e(2) e(2) -1 e(2) e(') e/(1)
-1 2 9 w2 w w2 W
e~') e(2) e,(2)
g w w2 1 W w2
C 3v E 2C 3z 3uy e(1} e"(I)
w
, e~l) _w 2 w -1 w2 -w :..,
D3 E 2C 3z 3Uy e~2) e~2) e,,(2) _w 2
-w w2 -1 W ::<:'
"0
'"
a, a, D6 E 2C 6z 2C 3z C 2z 3Uy 3Ux '"'
a2 a2 -1 C6v E 2C 6z 2C 3z C 2z 3uy 3u,
'"'"'"
a
e e 2 -1 0 D3h E 2S 3z 2C 3z Uz 3Uy 3ux !'?
(-) (-) o
i:l
a, a, a', 1 1 '"0
..,
T E 4C 3, 4C3~ 3C 2z a2 a2 a; -1 -1 'tI
0
b, b, a", -1 -1 1 -1
a ~r
e(1}
b2 b2 a~ 1 -1 1 -1 -1 1 Cl
w w2 e, e, e" 2 1 -1 -2 0 0 0
e(2) '"'
1 w2 w 1 (-) "0
(-)
3 0 0 -1
''""
e2 e2 e' 2 -1 -1 2 0 0
(-) (-) (-) (-)
~
w = exp(2ni/3) w
Table 3.6. (continued) ~
C4v E 2C4z C 2z 2ux 2uxy 0 E 8C 3 , 3C 2z 6C 4z 6Uxy

D4 E 2C 4z C 2z 2Uy 2Uxy 7d E 8C 3 , 3C2z 6S4~ 6uxy !-'
D2d E 2S 4z C 2z 2Uy 2uxy <:n
'<
a, a, 8
a, a, a, 1 1 a2 a2 1 1 1 -1 -1 8
~
..,
a2 a2 a2 -1 -1 e e 2 1 2 0 0 '<
b, b, b, -1 1 -1 t, t, 3 0 -1 1 -1 Cl
..,
t2 t2 3 0 -1 -1 1 0
b2 b2 b2 1 -1 1 -1 1
'0
e e e 2 0 -2 0 0 ''""
P>
:;
0-
>-l
:;-
!!
.., .
~
(Ij
Cs E Cs C~ C~ C 4S C sv E 2Cs 2C~ 5a '0
..,
(Ij
(Ij
'"
1 1 1 1 :;
a al ~
P p2 p3 p4 a2 1 -1
p4 p3 p2 -u 0
o
:;
P el 2 u-l
e 1) p2 p4 p3 2 -u u-l 0 '"
=f: P e2
e 2) p3 P p4 p2
P = exp(2ni/5) u= (v5+ 1)/2
Y E 12Cs 12C~ 20C3 15C2
a 1 1
tl 3 u l-u 0 -1
t2 3 l-u u 0 -1
g 4 -1 -1 0
h 5 0 0 -1
3.7 Representations of Point Groups 65
two-dimensional and t for three-dimensional. The letter a(b) denotes an irrep in

which rotation about the main axis (if there is one) through the smallest possible
angle is mapped by 1 (-1). The principal axis is assumed to be directed along
the Z-axis. The symbol of an irrep which is even (odd) with respect to reflection
plane is appended by one (two) prime(s). The symbol of an irrep that is even
(odd) relative to the inversion operation includes a subscript g(u). Pairs of com-
plex conjugate one-dimensional irreps are unified in two-dimensional reps and
are denoted by e since they form physically irreducible reps (Sect. 3.5.3).
Table 3.6 contains the irrep characters of 24 of the 32 crystallographic
point groups. The other eight crystallographic groups and Y h groups and
groups Cs, C sv and Yare the direct products of the considered point groups
and the inversion group Ci :
C4h = C4 X Ci , C6h = C6 X Ci , D2h = D2 X Ci ,
D4h = D4 X Ci , D6h = D6 X Ci , D3d = D3 X Ci , (3.7.1)

T,. =TxCi , Oh = 0 X Ci ,
The direct product G x Ci has twice as many conjugate element classes and
irreps as the group G. The character table of G x Ci irreps is easily obtained
from the characters of groups G and Ci . Half of the classes of G x Ci coincide
with the classes S of G. The rest are obtained by multiplication of classes S by
the inversion I: IS. Both S and IS classes of G x Ci in the irreps of G x Ci that
are even with respect to inversion have the same characters as S in G. These
irreps of G x Ci are labeled by the same symbol as the corresponding irreps in
G but with a subscript g. If in the obtained irreps the characters of the classes IS
are multiplied by - 1 we have the characters of odd irreps of G x Ci . They are
denoted by a subscript u.
Just under the rows with the characters of multidimensional irreps are the
symbols of irrep matrices for generators. The matrices themselves are given at
the bottom of Table 3.6. The representatives of classes indicated in the table are
chosen as generators.
Finally, in Table 3.7 information about irreps whose rep space is spanned
by the components x, y, z of a radius vector and by their quadratic combinations
is given. The matrices of these irreps may be easily calculated by using the trans-
formation properties of these basis functions.
All the point groups are subgroups of the full orthogonal group 0(3). The
subduction of irreps of 0(3) D~) and D~j), with integralj, on the elements of some
point group G c 0(3) is, in general, reducible. The subduction may be decom-
posed into irreducible reps with the usual methods of representation theory of
finite groups (Sect. 2.2).
The spinors transform under the operations of point groups G according to
the double-valued reps. This kind of rep arises upon restricting the irreps of 0(3)
D<j) with half-integral j to elements of G. The concept of a double group G is
useful for the generation of double-valued irreps of G and for the decomposition
of reducible double-valued reps of G into irreducible ones.
Table 3.7. Irreducible spaces spanned by the coordinates x,y, z and their quadratic combinations
Ci C2 Cs C 2h C2v D2 C4v D4 D 2d T 0 Td Y
x au b a' bu b, b3 e e e t, t2 t,
Y au b a' bu b2 b2 e e e t, t2 t,
z au a a" au a, b, al a2 b2 t, t2 t,
C3 C 3v D3 C4 S4 C6 C 3i C 3h D6 C 6v D3h Cs Csv
x-iy
x+iy
ell)
e(2)
e
e
e
e
e(l)
e(2)
e(1)
e(2) er
e 2)
e(1)
e r2)
u
e'(')
e,(2)
e,
e,
e,
el
e'
e'
et
e 2)
el
e,
Z a a, a2 a b a au a" a2 a, 02 a a,
Ci C2 Cs C 2h C 2v D2 C 4v D4 D 2d T 0 Td Y
yz ag b a" bg b2 b3 e e e t2 t2 h
zx ag b a" bg b, b2 e e e t2 t2 h
xy ag a a' ag a2 b, b2 b2 b2 t2 t2 h
x 2 _y2 ag a a' ag a, a b, b, b1 e e e h
3z 2 -r 2 ag a a' ag a, a a, a, al e e e h
x 2 +y2,Z2 ag a a' ag a, a a, a, a,
C3 C 3v D3 C4 S4 C6 C 3i C 3h D6 C 6v D3h Cs C Sv
x 2 +y2,Z2 a a, a, a a a a a' a, a, aj a a,
d+
r
zx-izy
ell)
e(2)
e(1)
e
e
e
e
e
e
b
b
e(1)
b
b
e(1)
ef
e I)
e ')
e
ef2)
efl)
f,) e'(')
e,(2)
e"(')
e2
e2
e,
e2
e2
e,
e'
e'
e"
er
e 2)
e ')
e2
e2
,
el
e(2) e(2) e(2) e(2) ef2) e,,(2) e" e/2)
zx+izy e e g e, el el
d =x 2 -y22ixy
Consider for a given point group G of order nG a double group G of order

nG = 2nG consisting of the elements of 0(3). Every element g EGis mapped by
two elements in G: g and g = gE. Denote by Cn, C;;1, C;;1, Cn the rotations about
the main axis through the angles 2n/n, 2n(n - l)/n, -2n/n, -2n(n - l)/n; by
C2 (U) and C 2 (U) the rotations through nand -no
The composition laws for groups 0 and D6 are given in Tables 3.8 and 3.9.
The numerical notation for symmetry elements is used. The symbols of elements
R corresponding to the numbers are given in the third column of each table. The
second column contains the coordinates onto which the point x, y, z (or x', y',
z) moves under the operation R. All the operations in the group D6 are ex-
pressed in the hexagonal system of coordinates: the axes x' and y' form an angle
of 2n/3 and the z-axis is perpendicular to the x' y' plane. In the left most column
of the tables the notations of the corresponding improper rotations IR are
gIven.
The same tables also give the composition law of double point groups 0
and 156 , The same numerical notations, but with and without overbars, are used
in double groups Gfor rotations differing by an angle 2n. In single groups 0 and
Table 3.8. Notations of elements and multiplication table of the point groups 0 and Oh
I xyz E 2 3 4 5 6 7 8 9 10 II 12 13 14 15 16 17 18 19 20 21 22 23 24
CTx xyz C 2x 2 T 4 3 6 5 8" 7 10 9 12 IT 14 13 16 15 18 17 20 19 22 21 24 23
CT y xyz C 2y 3 4 T 2 '7 8 5 6 11 12 9 10 15 16 13 14 19 20 17 18 23 24 21 22
CT= xyz C2= 4 3 2: T 8 7 6 5" 12 IT 10 9 16 15 14 13 20 19 18 17 24 23 22 21
S61 yzx C-311 5 8 6 '7 9 12 10 IT T 4 2 3 17 20 18 19 21 24 22 23 13 16 14 15
S62 yzx C-321 6 '7 5 8" 10 11 9 12 2 3 T 4 18 19 17 20 22 23 21 24 14 15 13 16
S63 yzx C-331 7 6 8 5 II 10 12 9 3 2: 4 T 19 18 20 17 23 22 24 21 15 14 16 13
S64 yzx C3~ 8 5" '7 6 12 9 11 10 4 T 3 2 20 17 19 18 24 21 23 22 16 13 15 14
S-1 zxy C 31 9 11 12 10 T 3 4 2: 5 7 8 6 21 23 24 22 13 15 16 14 17 19 20 18
61
S-1 zxy C 34 10 12 11 9 2 4 3 T 6 8 '7 5 22 24 23 21 14 16 15 13 18 20 19 17
64
S-1 zxy C 32 II 9 10 12 3 T 2 4 '7 5 6 8" 23 21 22 24 15 13 14 16 19 17 18 20
62
S-1 zxy C 33 12 10 9 11 4 2: T 3 8 6 5" '7 24 22 21 23 16 14 13 15 20 18 17 19
63
CT
xy yxz U XY 13 15 14 16 21 TI 22 24 17 19 18 20 T 3 2 4 9 11 10 12 5 '7 6 8
S-l
4= yxz C 4z 14 16 13 15 22 24 21 23 18 20 17 19 2: 4 T 3 10 12 9 11 6 8 5 7
S4z yxz C-4z1 15 13 16 14 23 21 24 22 19 17 20 18 3 T 4 2: 11 9 12 10 '7 5" 8 6
CTxy yxz U XY 16 14 15 13 24 22 23 21 20 18 19 17 4 2 3 T 12 10 11 9 8" 6 '7 5
(ljiz xzy U yz 17 18 20 19 13 14 16 15 21 22 24 23 5" 6 8 7 T 2: 4 3 9 10 12 IT w
xzy U yZ 18 17 19 20 14 13 15 16 22 21 TI 24 6 5 '7 8 2 T 3 4 10 9 11 12 :...
CTy=
S-1 :;.:I
4x xzy C 4x 19 20 18 17 15 16 14 13 23 24 22 21 7 8" 6 5 3 4 2 T IT 12 10 9 CD
'0
S4x xzy C-4x1 20 19 17 18 16 15 13 14 24 23 21 22 8" '7 5" 6 4 3 T 2: 12 IT 9 10 Cil
(liz zyx Vxz 21 24 23 22 17 20 19 18 13 16 15 14 9 12 11 10 5 8 7 6 T 4 3 2: 1!i
S4y zyx C-4y1 22 23 24 21 18 19 20 17 14 15 16 13 10 11 12 9 6 '7 8 5" 2 3 4 T aa
CTxz zyx Uxz 23 22 21 24 19 18 17 20 15 14 13 16 IT 10 9 12 '7 6 5 8 3 2: T 4 o
i:l
S-1 zyx C 4y 24 21 22 23 20 17 18 19 16 13 14 15 12 9 10 11 8" 5 6 '7 4 T 2 3
4y '"o
....,
"tI
o
a'
Cl
o'"
=
"5l
a,
-..\
Table 3.9. Notations of elements and multiplication table of the point groups D6 and D6h a-
co
I x' y' z E 1 2 3 4 5 6 "7 8 9 10 11 12

S-I
3z x'- y' x' Z C 6z 2 3 4 5 6 I 8 9 10 11 12 "7 !--'
S-I (Il
6z y' x' -y' Z C 3z 3 4 5 6 I 2: 9 10 IT 12 "7 8 '<
(iz x' )i' Z C 2z 4 5 6 I 2: 3" 10 11 12 "7 8 9
S6z y' - x' x' Z C- I3z 5 6 I 2: 3" 4 IT 12 7 8 9 10 ~
S3z y' y' - X' Z C-6z1 6 I 2: 3" 4 5" 12 "7 8 9 10 IT Q
(iy x' -y' )i' z Uy "7 12 11 10 9 8 I 6 5 4 3" 2: Cl
(3
(i _ x' x ' - y' Z U _ 8 7 12 IT 10 9 2 I 6 5 4 3
xy xy
(i_ y' x' Z 9 8 "7 12 11 10 3" 2 I 6 5" 4 "51'"
yx II>
u_yx
::;
(ix y'-x' y' Z Ux 10 9 8 7 12 IT 4 3" 2 I 6 5 Q..
(iyx x' y' -x' Z U yX 11 10 9 8 7 12 5 4 3 2: I 6 ;l

(ixy )i' x' z U XY 12 11 10 9 8 7 6 5" 4 3" 2: I ~.
....
::tI
~
'"
iii
a!:?
o
::;
'"
3.7 Representations of Point Groups 69
D6 these symbols correspond to the same rotation. As the inversion I and the
element E commute with any rotation in both single and double groups it is
easy to find from Tables 3.8 and 3.9 the product of any elements in the groups
Oh = 0 XCi' D6h = D6 XCi' Oh' D6h and any of their subgroups, e.g.,
Uxy S61 = IUxyC:;{ = IC4y = Si; ,

(3.7.2)
S4ZUyz = ICi; EIUyz = ECi; UyZ = EC31 = C31
As in 0(3), the elements E and E form in G an invariant subgroup H. The
factor group GIH is isomorphous to G.
Consider the irreps of the group G. Those of them for which the elements g
and (j are mapped by the same matrix correspond to the ordinary (single-valued)
irreps of the group G. Those irreps of G for which the matrices of elements g
and (j differ in sign generate the double-valued irreps of G. As we shall see, the
group G has no other irreps.
We write down the decomposition of the group G into left cosets with
respect to the invariant subgroup H:
nG
G= L gjH
j=l
(3.7.3)
and apply the method of the little group (Sect. 2.3.4). The group H has two
irreps: unit irrep a (with characters 1, 1) and rep b (with characters 1, -1). Each
of them forms one ray star. The little group is G itself for both irreps a and b of
H.
Consider the reps of G connected with the unit irrep a of H (of type a). In
this case every irrep of the factor group GIH +-+ G generates an irrep of little
group G for which the matrices of elements 9 and g coincide. It is obvious that
these irreps of G correspond to single-valued irreps of G.
Now consider the reps of G related to the irrep b of H (of type b). The reps
of H subduced from these irreps of G are in general reducible and contain only
the irrep b (one or more times). Therefore the element E is mapped in these
irreps by minus the identity matrix ( - E). Each of these irreps of G generates a
double-valued irrep of G. The coset representatives in (3.7.3) do not form a
group. Therefore the generation of irreps of the group G reduces to the genera-
tion of projective reps of the factor group GIH isomorphous to G with a factor
system
I, if gjgj' = gjj' ,
w(gj' gj') = { -1, (3.7.4)
if gjgj' = gjj' .
For a given factor system the generation of projective irreps of GIH in any
actual case is not a difficult problem. The matrices of projective irreps for
elements gj are at the same time the matrices for corresponding elements of Gin
the irreps to be found. The matrices of elements gjE = gj differ from them only
in sign. These two matrices differing in sign correspond to the element 9 in the
double-valued irrep of G. The dimensions nOt of double-valued irreps of G coin-

cide with the dimensions of the corresponding projective irreps and satisfy the
relation
(3.7.5)
The number of double-valued irreps of G is equal to the number of type b irreps

of G. This may be established as follows. The group G(G) has kG(kG) irreps
where kG(kG) is the number of classes in G(G). The number of irreps of type a is
kG' The number of b type irreps and therefore the number of double-valued
irreps of G is equal to kG - kG'
The partition of the elements into classes is made in the usual way. The
elements E and E form classes themselves. The same may be said about elements
I and i if they are in G. If an axis is bilateral then the rotations Cn and C;l, C;l
and Cn are conjugate.
Table 3.10 contains the character tables of b type irreps of eleven double
point groups of pure rotations. Other crystallographic double point groups are
either isomorphous to those in Table 3.10 or are their direct products with the
inversion group Ci . Table 3.5 may also be used for double groups, however, the
groups C;, 56' CZh , 153d are not isomorphous to Cz , C6 , 15z , 156 , respectively.
Taking into account time reversal symmetry the irrep b of the group C3 should
be double.
3.8 Representations of Space Groups
3.8.1 Irreducible Representations of the Translation Group. The Brillouin Zone

The group T of pure translations (E 1a,,) of an infinite lattice is a group of infinite
order. By introducing cyclic boundary conditions (Sect. 3.3.2) one assumes that
the infinite crystal consists of blocks in the form of parallelepipeds having sides
Al = N1a 1, A z = Nza z, A3 = N 3a 3 It is assumed that the points of different
blocks connected by translations A" = Lt=l n;Ai are physically equivalent, i.e.,
(ElaJN j = (EIAj) = (EIO). The large positive number N = N 1N zN 3 defines the
size of each block also called the main region of a crystal (this block contains N
primitive unit cells in the cyclic model of a crystal). Only the finite order group
T(N) (modulo translations A1 , A z, A 3 ) of N translations a" = Lt=l n;a; inside
the main region is considered when generating the irreps of the translation
group. Because this group is Abelian all its irreps are one-dimensional. More-
over, the group T(N) is a direct product of groups T(N,), T(N 2 ) and T(N 3 ), as all
the translations (Ela,,) commute. Each group T(N;) of N; translations (Eln;a;)
has N; one-dimensional irreps D(j)((Eln;a;)), j = 1,2, ... , N; satisfying the con-
dition [D(j)(Ela;)]N; = D(j)((EIN;a;)) = D(j)((EIO)) = 1. Taking D(j)[(Elai)] =
exp( - 2nip) N;) (where Pj is an integer) one satisfies this condition. The integer
Pj = 0, 1, ... , N; - 1 (i = 1,2,3) denotes different irreps of the translation group
Table 3.10. Irreducible representation (of type b) characters of proper double point groups
CI E if C3 E C3 C;-I if C3 C31
a -1 e(l) _w 2 w -1 w2 -w
e(2) -w w2 -1 W _w 2
Ii -1 -1 -1
w = exp(2rri/3)
C2 E C2 if C2 C4 E C4 C2 c.. 1 if C4 C2 c.. 1
-(I)
el -1 -i -(1)
el v iv -1 -v -i -iv
-i -(2)
-(2) -1 el {~ -iv -i -v -1 iv v
el
-(I)
e2 IV -i v -1 -iv -v
-(2)
e2 t -v -iv -1 v -i iv
v = exp(irr/4)
w
C6 E C6 C3 C2 C:;-I C;;I if C6 C3 C2 C31 C;;I 00
:>;I
_w 2 -i -w "0
e-(I)
l -iw w -iw 2 -1 iw w2 iw 2 "...
-(2) _w 2
el iw 2 -w -i w2 iw -1 -iw 2 w -iw ""'":>
-(I) t -i -i -1 -i
e2 -1 -1 g
e~2)
O
{~ -i -1 -i -1 -i -1 :>
-(I)
e -iw 2 -w w2 -iw -1 iw 2 -w -i _w 2 IW '"0
3 ....,
-(2) _w 2 _w 2 tZl
e3 iw -i W iw 2 -1 -iw -w -iw 2 "0
~
t W= exp(2rri/3)
~
Cl
...
0
~
15 2 E if Z'
C2 C2 , C 2y , C2y C 2x , C2x 15 3 E E C 3=' C 3=! C 3=, C:;-~ 3Uy 3Uy
E 2C 2 , 2C 2x E E 3Uy 3Uy
"5l
E 2C 2y 2C 3 = 2C 3 =
-(11
e 2 -2 0 0 0 e! -I -I -i ;::
e-(21
l {: -I -I -I
tJ 2 2 -2 -I 0 0
Table 3.10. (continued)
-.)
154 E E 2Ux ,2Ux 2UXy ,2UXY N
C2 " C 2 , C 4 " C 4: C 4 " C 4:
E E 2C 2 , 2C 4 , 2C4 , 4Ux 4UXY
w
e, 2 -2 0 h -J2 0 0 C/).
e2 2 -2 0 0 0 '<
-J2 J2 9
9
156 E E C 2,' C 2, C 3" C 3: C 3" C 3; C 6 " C(;; C 6" C(;; 3Ux ,3Ux 3Uy ,3Uy '<
-"...
E E 2C 2 , 2C 3 , 2C 3 , 2C 6 , 2C 6 , 6Ux 6Uy
...Cl
0
~
e, 2 -2 0 1 -1 -J} 0 0 '0
J1 V>
2 -2 0 1 -I 0 0 ~
e2 -)3 )3 ::s
-2 -2 2 0 0 0..
e3 2 0 0 0
"'l
::s-
!li.
T E E 3C 2" 3C 2, 4C 3 4C 3 4C:J' 4C 3'
...
:>:I
E E 6C 2, 4C 3 4C 3 4C:J' 4C 3' '0
"<l
V>
e 2 -2 0 -1 -1 "::s
{(II -2 0 w -w _w 2 w2 ~
{(2I g -2 0 w2 _w 2 -w w
o
::s
V>
IV = exp(2rri/3)
i5 E E 4C 3 .3C 3' 4C 3 ,4C 3' 3C 2" 3C 2 , 3C 4 " 3C4; 3C4 " 3C 4; 6Uxy ,6Uxy
E E 8C 3 8C 3 6C 2 , 6C 4 , 6C4 , 12Uxy
e, 2 -2 -I 0 h -h 0
e2 2 -2 -I 0 0
4 -4 -1 J 0
-J20 J20 0
I
y E E 6Cs, 6C i l 6C~,6Ci2 6C, 6C i 3 6c1,6C S 4 10C3 ,10C 3- 1 IOC~, 10Ci 2 15C2,15Cil
E E 12Cs 12C~ 12C~ 12C1 20C3 20C 3 30C2
e1 2 -2 u -u u-l l-u -1 0
e2 2 -2 l-u u-l -u u -1 0
(j 4 -4 1 -1 -1 1 -1 1 0
[ 6 -6 -1 1 -1 0 0 0
u= (Vs+ 1)/2
3.8 Representations of Space Groups 73
T(N;). The irrep D(P1P2P3)((Ela,, of the translation group T(N) can be written as
D(Pt P ZP 3)Elan )) = exp [-2ni(pjn j INj +P2n2IN2+P3n3IN3)] . (3.8.1)
There are N = Nl N2N3 sets of integers Pi> P2' P3 (Pi = 0,1, ... , Ni - 1) which are
used to label N different irreps of the translation group T(N).
Introducing the primitive translation vectors B 1 , B 2 , B3 of the reciprocal
lattice by
(i,j = 1,2,3) , (3.8.2)
one may define allowed k-vectors (wave vectors) by k = x1B1 + x 2B2 + X3B3
where Xi = pjNi (i = 1,2,3). Thus
(3.8.3)
so that
I D(k>((Ela,, = exp(-ik'a,,) (3.8.4)
The N irreps of T(N) are now labeled by the N allowed k-vectors. The point
symmetry of the reciprocal lattice coincides with that of the direct one. How-
ever, the type of the reciprocal lattice may differ from that of the direct lattice.
Adding the reciprocal lattice vector
(3.8.5)
to the allowed k-vector we have
exp( -i(k + Bm)a,,) = exp( -ik a,,)exp( -iBma,,)

= exp( -ika,,) . (3.8.6)
A pair of vectors k and k' = k + Bm are said to be equivalent since the irrep of
T(N) described by k can be equally well described by k'.
The basis functions for the irreps of the translation group T(N) are known as
Bloch functions cp(k, r) and may be written in the form
I cp(k, r) = exp(ik' r) U (k, r) I (3.8.7)
where U(k,r) = U(k,r + a,,). Indeed

t"cp(k, r) = exp( - ik . a,,) exp(ik . r) U (k, r - a,,)
= exp( - ik a,,)cp(k, r) . (3.8.8)

The Bloch functions are also called the k-basis. The label k is determined up to
within a reciprocal lattice vector [as in (3.8.6)] and can be changed by vectors
B Iff of the reciprocal lattice.
Applying a space group operator {J == {Rlv} ({J E G) to the Bloch function
cp(k, r) we obtain a Bloch function ip(Rk, r). Indeed
{Elan} {Rlv}cp(k,r) = {Rlv} {EIR-1a.}cp(k,r)
= exp ( - i k . R - 1 an )( R Iv) tp (k , r)
=exp(-iRk'an){Rlv)tp(k,r) ,
i.e.,
{Rlv}cp(k,r) = ip(Rk,r) . (3.8.9)
The allowed k-vectors occupy a region in the reciprocal lattice called the
Brillouin zone. The latter is defined as consisting of all those points of k-space
that lie closer to k = 0 than to any other reciprocal lattice point. Its boundaries
are therefore the planes that are the perpendicular bisectors of the lines joining
the point k = 0 to the nearest and sometimes to the next-nearest reciprocal
lattice points (the planes bisecting the line from k = 0 to k = Bm have the equa-
tion k BIff = IB... 12 /2). For some lattices (body-centered cubic, for example) only
nearest-neighbor reciprocal lattice points are involved in the construction of
the Brillouin zone but for others (face-centered cubic for example) next-nearest
neighbors are involved as well.
By construction the Brillouin zone contains N allowed k-vectors when N
primitive unit cells are included in the main region of a crystal. As the number
N is assumed to be arbitrarily large, in the limiting case of N -+ 00 the allowed
k-vectors take all values inside the Brillouin zone.
The Brillouin zone is the Wigner-Seitz unit cell of the reciprocal lattice
exhibiting the point symmetry of the reciprocal lattice. Monoclinic and triclinic
space groups are an exception to this; there the primitive unit cell of the recipro-
cal lattide is used for the Brillouin zone. For most lattices the shape of the
Brillouin zone is unique while for others there are two or more possible shapes
depending on the relative lengths of the primitive translations and the angles
between them [3.6].
Two vectors k and k' were said to be equivalent if k' = k + B .... By defini-
tion no two interior points of a Brillouin zone can be equivalent; but every point
on the surface of the Brillouin zone has at least one equivalent also on the
surface of the Brillouin zone.
Those elements of the point symmetry group P of the reciprocal lattice
which transform a point k into itself or into some equiv.alent k-point form the
wave-vector symmetry point group P k !: P. For example, the point group P k
of the k-vectors r, Z, M, A (Fig. 3.6) for a simple tetragonal lattice coincide
with the D4h point group of the tetragonal lattice itself; the point group DZh
of the k-vectors X and R is a subgroup of D 4h
Fig. 3.6. The BriJIouin zone for a simple tetragonal lattice
All the mentioned points of the Brillouin zone are called points of symme-
try. By definition, k is a point of symmetry if there exists a neighborhood of k in
which no point k' has the same symmetry group PIc and PIc' c: PIc' The r (k = 0)
point of the Brillouin zone is usually a symmetry point; exceptions here are the
space groups of the crystallographic classes Cs' Cnv , Cn. All the other symmetry
points are situated on the surface of the Brillouin zone and are usually denoted
in a more or less unique way by capital Roman letters as in Fig. 3.6 for a simple
tetragonal lattice. Kovalev [3.7], however, used ordinal numbers to denote k-
vectors. For example, the correspondence between the generally accepted and
Kovalev's notations of the symmetry points on Fig. 3.6 is r~k17' Z ~k19'
M ~k18' A~k20' X ~k15' R~k16'
If in any sufficiently small neighborhood of k there is a line (plane) of points
passing through k and having the same point group PIc then k is said to be on a
line (plane) of symmetry. The lines of symmetry are denoted both by Roman (on
the surface of the Brillouin zone) and Greek (inside the Brillouin zone) capital
letters. A symmetry line may be denoted by two symmetry points at the ends
of this line: rM -17(C2v ), rx +-+ L1 (C2v ), rz +-+ A (C4v ), MX +-+ Y(C2v ), AR +-+
T(C 2v ), ZA ~ S(C 2v ), MA ~ V(C 2v ), ZR ~ U(C 2v ) (Fig. 3.6); the corresponding
PIc groups are in parentheses. It is evident that the point groups C2v of differ-
ent wave vectors, being isomorphic to each other, do not coincide for all sym-
metry lines. For example, the second order symmetry axis C2 is along the
X-coordinate axis for a Lf-line and along the XY-symmetry axis for a .E-line.
In the tables of [3.2] the coordinates of symmetry points and symmetry
lines in k-space are listed with respect to the reciprocal lattice primitive transla-
tion vectors: k = IIBI +x2B2+x3B3'
For each Brillouin zone there is a basic domain Q such that LREPRQ
is equal to the whole Brillouin zone where R are the elements of the holo-
symmetric point group P of the relevant crystal system. In the case under con-
sideration R E D4h and the Q volume is equal to 1/16 of the Brillouin zone
volume (Fig. 3.6).
3.8.2 Stars of Wave Vectors. Little Group.

Full Representations of Space Groups
The representation theory of space groups uses a theorem that the translation
group T is an invariant subgroup of G (T <J G; Sect. 3.3.1). Therefore the little
group method (Sect. 2.3.4) may be used for the generation of irreps.
Let us suppose that D(g) is an irrep of G acting in a space L of dimension
n. The operators D(g) for g = (Elan)ET form a rep of T which is in general
reducible. Let it contain irreps of T characterized by the vectors k = k j , k2' ... ,
k n Therefore a basis can be found in space L which consists of Bloch functions
cp(k l ' r), ... , cp(kn' r). With respect to this basis the elements of T are represented
in the irrep D(g)~by diagonal matrices with elements exp( - ik p all), P = 1,2, ... ,
n. The fact that D(g) is a rep of G implies that if we start with cp(k, r) and generate
the Bloch functions {Rlv}cp{k,r) = iP(Rk,r) where (Rlv) E G then we obtain
some linear combination of the n Bloch functions of the initial basis. This means
that Rk is one of the vectors k, k2' ... , kn- Moreover the space L of dimension n
is irreducible under D(g) for all 9 E G. Therefore, as we run over all elements of
G operating on cp(k, r) by D(g), we generate the entire space L, i.e., each of the
vectors k 1, ... , k n appears as the transform of k under some element of the point
group F (point group of the space group G). It may be that the vectors kb ... ,
k n are not all different. A set of ns distinct (nonequivalent) k vectors chosen from
the set k l ' ... , k n is called the star of wave vector k and is denoted as *k. A star
can be generated from one of its members by operating on it by elements of
point group F.
The point group of the wave vector k (little co-group of k) Fk !;;; F, by
definition, consists of all the rotations or reflections R!k) (i = 1,2, ... , nk) that
rotate k into itself or an equivalent vector R!k)k = k + Bm.
In Sect. 3.8.1 there were defined points and lines of symmetry in the
Brillouin zone for the case when F = P [holosymmetric space groups (in partic-
ular Dl:)]. In the same manner the points and lines of symmetry may be defined
for the point group F c P. Then, instead of the basic domain Q of the Brillouin
zone defined in Sect. 3.8.1 we may introduce the representation domain J ;:> Q
of the Brillouin zone such that LREFRJ is equal to the whole Brillouin zone (J
is also called the irreducible part of the Brillouin zone for the space group G). If
a symmetry point group F of a crystal class coincides with a symmetry point
group P of a crystal system the representation and basic domains are the same
as in the case of the space group Dl:.
We can write F as a sum ofleft co sets with respect to the subgroup Fk :
ns
F = L R;Fk
;=1
, (3.8.10)
where ns = nF/nk is the number of k-vectors in the star *k. If R;k = k; then all
elements of the left coset R;Fk transform k into k;.
By definition, the little group Gk of wave vector k consists of all elements
gj(k) -
- (R(k)1
j Vj(k) + all ).
,} -
- 1, 2, ... , nk were
h R(k)
j E Fk. Th e group Gk c G IS
. a
space group of order Nnk so that we can write G as a sum of left co sets with
respect to the subgroup Gk (this decomposition has the same form for a model
of an infinite crystal with the translation group T of infinite order):
ns
G= L gjGk ,
j=l
(3.8.11)
Any element of coset (Rjl vj)G k transforms a Bloch function CfJ(k, r) into a
Bloch function CfJ(kj , r). Thus, if the vectors k, k2' ... , k n characterizing the rep
D(g) of dimension n = nans are not all unique, then the star k, k2' ... , kns is
repeated exactly na times in the set k, k2' ... , k n. Let the basis set of space VI) be
formed by Bloch functions CfJ~a)(k, r) (i = 1,2, ... , na)' These functions form a basis
of a so-called small (allowed) irrep of the space group Gk :
n,
D(g)CfJ~al(k, r) = L DI,~,a)(g)CfJI;Zl(k, r) , (3.8.12)
i'=l
The wave vector k is called a canonical wave vector.

Not all the irreps of space group Gk are small irreps of this group since the
small irrep basis functions CfJla)(k, r) (i = 1,2",., na) have an additional property:
they are Bloch functions with the same vector k, i.e., the matrices of the small
irrep are diagonal for the pure translations (Ela,,) and have na equal diagonal
elements exp( - ik 'a,,). The Bloch functions CfJi(kj , r) == {Rjl vj } CfJi {k, r) form the
basis set of irrep k j = Rjk of the translation group T The space group ele-
ments g(k j ) = gjg(k)gj-1 form the group Gkj of the wave vector k j . The point
group Fk consists of elements R(k j ) = RjR(k) Rj- 1. The basis functions CfJi(kj , r)
(i = 1, 2,.~., na) of a space L(j) transform over the irrep D(k,a)(gj-1 g(kj)gj):
g(k j )CfJi (kj , r) = gA(k)CfJi(k, r)
= L DI,~,a)(g(kCfJi,(kj' r)
i'
(3.8.13)
The space L = Lj L (j) of nsna functions CfJi(kj , r) (i = 1, ... , na; j = 1,2, ... , n.)
is irreducible under G. These functions form a basis of the so-called full irrep
D(*k,a) (g) of the space group, The full irrep D(*k,a)(g) of G is induced by the small
irrep D (k,a)(g) of the little group Gk E G: D(*k,a) = D(k,a)jG,
(*k,a)()
D i'j',ij g = D(k,a)(
i'i gj"-1
ggj ) Uj"j'
..
. (3.8.14)
The little group Gk is itself a space group, The small irreps of Gk can be
found if projective irreps of the point group Fk are known.
3.8.3 Small Representations of a Little Group.

Projective Representations of Point Groups
The small reps of little groups are sufficient for many purposes in solid state
theory, such as classifying states within electron energy bands and vibration
frequencies within phonon band spectra, and for generating the symmetry-
adapted wave functions.
The little group Gk is itself a space group. Whereas in the reps of G the
translation (Ela ll ) is represented by a diagonal matrix, in the small irreps D(k,lX)
of Gk that we are looking for (Ela,,) is represented by a scalar matrix
D(k,IX)((Ela ll )) = exp(-ik'all)E nka , (3.8.15)
where nka is the dimension of the small irrep D(k,lX) and Enka is the unit matrix of
order nka'
We decompose Gk into left cosets with respect to the translation group T:
(3.8.16)
The coset representatives in (3.8.16) obey the multiplication rule
(3.8.17)
where
and (3.8.18)
Because a ij is a translation it follows that
(3.8.19)
If we now set for all 9 E Gk
I D(k,IX)(g) = exp( - ik v)jj(k,IX>(R) I (3.8.20)
then from (3.8.19) we obtain

jj(k.IX)(Ri)jj(k,IX)(R) = exp( - iBi v)jj(k,IX)(R s ) , (3.8.21)
where the reciprocal lattice vector Bi is defined by the relation
Kilk = k + Bi . (3.8.22)
Equations (3.8.20~22) together imply that the matrices jj(k,IX)(R) are the
same for all members of any fixed coset in (3.8.16), i.e., these matrices are in
correspondence with the elements of the factor group Gk/T The factor group
Gk/T is isomorphic with the little co-group Fk so that jj(k,lX) is a matrix-valued
function on the elements of the point group of wave vector Fk with multiplica-
tion law
(3.8.23)
Matrices jj(k,a) form a so-called projective rep of the point group Fk with the
factor system
(3.8.24)
where B; is defined by (3,8.22).

We see from (3.8.20) that the small irreps D(k,a) of a little group are found
if the projective irreps jj(k,a)(R) of the point group Fk with the factor system
(3,8,24) are known,
When the space group G is symmorphic all the fractional translations Vj
may be chosen to be zero (Sect. 3,3.1) so that all the factors w(R;, R) = 1 and
jj(k.a)(R) coincide with the IXth irrep of the point group Fk. When k is an interior
point of the Brillouin zone or (Ri 1 k - k) .1 Vj for all R; and Vj in the group Gk
the projective irreps jj(k,a)(R) also coincide with the usual irreps of the point
group of a wave vector. However, for some points on the surface of the Brillouin
zone in the case of nonsymmorphic space groups the projective irreps jj(k,a) are
not the usual irreps of the point group F k
To find jj(k,a) with the factor system (3.8.24) Herring's approach [3.12] may
be useful. In this approach the problem is reduced to finding ordinary irreps of
abstract groups with order greater than that of Fk but not very large.
In [3.6] it is shown that these groups for different wave vectors in the
Brillouin zone of one space group or for the same wave vector in the Brillouin
zone of different space groups may be isomorphic. In [3.6] all the irreps of all
the abstract groups that occur among reps of space groups are completely
identified. In [3.13] the projective irreps jj(k,a) are generated and tabulated for
all the wave vector point groups and all the possible factor systems, In [3.2] the
small irreps of little groups are found from those of the translation group by
successive augmentations, each augmenting operator being chosen so that the
augmented group contains the unaugmented one as an invariant subgroup.
In Sect. 3.7 we have discussed the double-valued reps of the point groups,
The double-valued space group reps considered in the next section are necessary
when spin-dependent terms are included in the Hamiltonian of a crystalline
solid.
3.8.4 Double-Valued Representations of Space Groups

In the double space group G the rotation through 2n is no longer an identity
element E and 2 = E. The double group G of a space group G is given by the
coset decomposition
G= L RilvJT + (R;illvi)T)
i
; (3.8.25)
where R i , Ri = R;If = ERi are the elements of the double point group F and T
is the translation subgroup of the space group G. In the double space group G
there are two elements (RilvJ and (RilvJ corresponding to every element (R;lvi)
of the space group G. The translation subgroup T is an invariant subgroup of
the double space group G.
Because for any vector v in three-dimensional space Ev = v (any rotation E
through 2n does not change the vector v) the multiplication rule for the mem-
bers of the double space group G is
(R 1 Iv 1 )(R 2Iv 2) = (RIR2Ivl + R 1 v2) ,

(3.8.26)
(R 1 Iv 1 )(R2Iv 2) = (RIR2Ivl + R 1 v2) .
The theory of reps of a space group G given in Sects. 3.8.2, 3 is also applica-
ble to finding the reps of the double space group G. As for the wave vector
k = Ek, the double little group Ok consists of the elements g(k)eGk and g(k) =
Eg(k). The double point group Fk of the wave vector consists of all the
elements R(k)eFk and R(k) = ER(k).
The irreps of the space groups G and Gk are related in the same manner as
thdse of single space groups G and Gk (Sect. 3.8.2).
The full irrep jj(*k.P) of the double space group G is induced by the small
irrep jj(k.P) of the double little group Gk . The dimension n*k,p of the double-
valued rep jj(*k,P) is equal to nsnkp, where ns is the number of wave vectors in the
star *k and nkp is the dimension of the double-valued rep jj(k,P) of Gk . The
matrices of the full double-valued irreps jj(*k,P) have the same block structure as
the matrices (3.8.14) of the single-valued full irreps. However, one has to use for
both elements (Rlv) and (Rlv) of double space group G the double-valued small
irreps jj(l"P) instead of single-valued D(k,P) in (3.8.14).
The double little group Gk is itself a space group. The small irreps of Gk can
be found if projective double-valued irreps of the double point group Fk are
known.
Let the group H consist of the elements (E, E). The direct product T x H
is an invariant subgroup of the double little group Gk since the rotation E
commutes with all pure translations. All the irreps of the group T x Hare
one-dimensional and may be found as the direct products of the irreps of the
groups T and H. The element E in irreps of a (b) type is represented by 1 (-1).
Let the double group Gk be decdmposed into cosets:
"k
Gk = L (Rjlvj)T x
j=l
H , (3.8.27)
nk
Gk = I
j=l
[(Rjlv)T + (RjlvJT] (3.8.28)
The factor-groups Gk/(Tx EI) and GklT are isomorphic to the point
groups Fk and Fk, respectively. Subduction of the small irrep of the group Gk
on the subgroup Tx EI consists of the irreps of only one type (a or b).
In the irreps of type a (single-valued irreps) the element E of the group Gk is
represented by the unit matrix. In the b-type irreps (double-valued irreps) the
element E is represented by the negative unit matrix. To generate b-type irreps
the relations
i5(k)(Rjl v) = exp( - ik vj)D(Rj ) , (3.8.29)
i5(k)(Rjlvj) = -exp( -ik' v)D(R) (3.8.30)
may be used.
Applying the procedure considered in Sect. 3.8.3 one obtains that the
matrices D(RJ form the projective irrep of the group GklT x H (isomorphic
to the group F k ) with the factor system
for RjRj' = Rjj.

(3.8.31)
for RjRj' = Rjj'
where
(3.8.32)
In the same manner one obtains that D(R), D(R) (j = 1,2, ... , nk) form projec-
tive irreps of the double point group Fk with the factor system
w(Rj,Rj') = w(Rj,Rj') = w(Rj,Rj') = w(Rj,Rj') (3.8.33)
where w(Rj , Rj') is defined by (3.8.32).
3.8.5 Dependence of the Labeling of the Irreducible Representations

of a Space Group on the Setting
As we have seen, all the irreps of space groups can be induced from the small
reps of the little groups Gk As the induction procedure result does not depend
on the choice of the canonical wave vector k for the given star *k, the notation
for small irreps may be maintained for the corresponding induced (full) irreps of
the space group G. Therefore we discuss first the notation of small irreps.
The irreps of the space groups can be found in a number of reference books
[3.2,6, 7, 14]. Each of these reference books uses different space group settings
as well as different systems for labeling irreps. Choosing the setting means the
choice of both the origin and the orientation of the symmetry axes relative to the
translation vectors must be decided. The orientation may be different for mono-
clinic and hexagonal lattices. In [3.15] these reference books are compared and
some correspondences are obtained. To relate the different space group settings
it is necessary to transform a symmetry element g in the first setting into a
symmetry element g' in the other. Let go = (Rola o) be an operator which relates
a point r in the first setting with the same point r' in the second setting (r' = gor)
and let the symmetry element g (given in the first setting) act on the point
r: gr = r. The same symmetry element in the second setting g' acts as g'r' =
r' = gor. Therefore g' gor = gogr so that
(3.8.34)
The transformation operator go is given in [3.15] as the operator taking a point

(x,y,z) in the international setting [3.3] to one of the other four settings. For
example in the case of the space group Dl: the operator go is equal to, for [3.2]
(EIO); for [3.7] (Ela 2 /2 + a 3 /4); for [3.6] (Ela 3 /4); and for [3.14] (Elat/2).
The various authors who have studied individual space groups used various
labels for the small irreps. In [3.15] the compatibility relations (Sect. 3.8.6) were
used to devise a notation scheme. For example, the cubic space groups nota-
tions T 12 , T 1S convey in an obvious way the "A-content" of a T rep: T 12 1G,1 =
..11 + ..1 2 ; T 1 slG,1 = ..11 + ..15' There are, however, cases of ambiguity where
compatibility relations for one point do not suffice to specify the rep uniquely
(for example, in groups with a simple cubic lattice, M1 as well as M3 reps are
compatible with ..[1)'
In existing tables of small irreps [3.2, 6, 7, 14] integers are used to denote
different reps of the same group Gk If the inversion I is in this group the reps
with positive or negative unit matrix for the operation I have symbols with a
plus or minus. For example, these symbols are used in notations of Dl: space
group irreps for points T, M, R (Sect. 3.8.6): T 1+, T4- and so on. As a rule, the
reps in tables are ordered according to their dimension. In Kavalev's book [3.7]
the projective irreps D(R) of the wave vector point group Fk are given and
numbered. This must be taken into account when comparing the notations
given in [3.7] for small reps.
Unfortunately even if these simple rules of irrep notation are adopted the
different choices of origin can still lead to diverging notations. As an example we
consider the point A with kA = Bt/2 + B2/2 + B3/2 for the space group Dl:. All
nonzero characters of small irreps for this k-point group are given in Table 3.11
in the notation of [3.2].
Kavalev [3.7] gave projective irreps of the D4h point group for the point
k 20 ( = A). After multiplying by exp( -ik 2o ' v) we obtain Table 3.12 of the small
irreps in Kovalev's notation.
However, it is a mistake to directly compare these tables to relate the
notations of small irreps in the settings used in [3.2] and [3.7]. In fact, the
Table 3.11. Small irreducible representation of GA according to [3.2] (the

origin is at Wyckoff position a)
(EQIO) (QzIO) (U~yIO) (U~yIO) (O":yIO) (O":yIO)
Al 2 2 0 0 2 2
A2 2 2 0 0 -2 -2
A3 2 -2 -2 2 0 0
A4 2 -2 2 -2 0 0
Table 3.12. Small irreducible representation of G' 20 according to [3.7]
(EdIO) (C1zI0) (U~ylw) (U~)w) (O":ylv) (O"~ylv)
I, 2 2 2 2 0 0
I2 2 2 -2 -2 0 0
I3 2 -2 0 0 -2 2
I4 2 -2 0 0 2 -2
w = (1/2, 1/2, 1/2), v = (1/2, 1/2,0)
Table 3.13. Correspondence between the notations of small irreducible

representations of D!: according to (3.2, 7)
[3.6] [3.2] [3.7] E C 2z UXy U_xy O"xy 0"-

xy
Al Al I4 2 2 0 0 2 2
A3 A2 I3 2 2 0 0 -2 -2
A2 A3 I2 2 -2 -2 2 0 0
A4 A4 II 2 -2 2 -2 0 0
second table corresponds not only to a change of the origin a --+ d but also to
a change of the coset representatives [in the decomposition of (3.3.1)]. In-
deed, using (3.8.34) one obtains the following correspondence between the coset
representatives:
(C~zIO) = (EIO,I,O)(C~zIO) , (U;yIO) = (EIO, I, I)(u:ylw) ,
(U:yIO) = (ElI. I, I)(u:ylw) , (O";yIO) = (Ell, I,O)(O"':ylv) , (3.8.35)
(O"~yIO) = (EIO, I,O)(O"~ylv) .
The lattice translations (Ela,,) giving multipliers exp( -ik 2o ' a.) must be taken
into account.
Table 3,13 shows the correspondence between the notations of the small
irreps of the space group Dl: according to [3.2, 6, 7]. In the book edited by Zak
[3.14] the characters of the same reps are in error. The coset representatives
chosen correspond in fact to the space group Dll.
3.8.6 Example: Irreducible Representations

of Space Group D~t Compatibility Tables
In Sect. 3.8.1 we considered points and lines of symmetry in the Brillouin zone
of simple tetragonal lattice and space groups with F = D4h (where the represen-
tation and basic domains of the Brillouin zone coincide). In Table 3.14, the
labels of the corresponding k-vectors are in the notation of Miller and Love
[3.2] for small irreps oflittle groups for space group Dlt. The decomposition of
Dlt into left cosets with respect to the translation group T has the form of
(3.4.1).
The coset representatives (R Iv) are fixed by (3.4.1) and are those corre-
sponding to placing the origin at Wyckoff position a (Sect. 3.4.1). In Table 3.14
the characters of the space group irreps for these coset representatives indicated
by their orthogonal parts R E D4h are given.
For the r-point inside the Brillouin zone small irreps are labeled by the
irreps ofthe point group D4h ; in the first column the Mulliken notations of these
irreps are also given. The symmetry points M, Z, A, R, X lie on the surface of
the Brillouin zone (Fig. 3.6) and the small irreps are connected with projective
irreps of the point groups D4h and D2h . The M, Z and A stars consist of one ray
so that for these wave vectors small irreps are the full group irreps. The stars *X
and *R consist of two rays: (0,1/2,0), (1/2,0,0) and (0,1/2,1/2), (1/2,0,1/2) re-
spectively. For these stars.the point group of the wave vector F" = D2h includes
the following rotations and reflections: Ux , Uy, C 2z , I, uX, uy, U z The decomposi-
tion of the space group Dlt into left cosets with respect to the G" may be written
as
(3.8.36)
The elements of the coset (C';-; 10, 0, O)G" transform wave vectors X(1)(O, 1/2,0)
and R(l)(O, 1/2, 1/2) into wave vectors X(2)(1/2, 0, 0) and R(2)(1/2,0, 1/2), respec-
tively.
In Table 3.14 small irreps d(",a) of little groups G(X(l) and G(R(l) are also
listed. To find the corresponding full group Dlt irreps D(*",a) one needs to use
(3.8.14), the relation between matrix elements of the small and induced irreps for
n = 2. As the wave vector groups G(X(l) and G(R(l) are invariant subgroups of
the space group Dlt (as any subgroups of index 2) gj-:l g(")gj E G" only for j' = j.
Therefore the full group irreps D(*",a)(g) have nonzero blocks on the main diago-
nal only for the elements of G". Taking into account that
C4 AUx , Uy , C2z )C';-zl = (Uy , Ux , C2z )
and that the inversion I commutes with all the point group operations one
obtains the following form ofthe full group irrep matrices D(*",a)(g) for *k = *X,
*R (v = (1/2, 1/2, 1/2)):
(3.8.37)
Table 3.14. The characters of the small irreducible representations of the space group Dl:
r E UxU, C 2z C 4z C 4; U 3i,UX ' I (Jxay Uz S4;S4Z (Iiy(Jxy
al 1+ 1 1 1 1 1 1 1 1 1 1
big 2+ 1 1 1 -1 -1 1 1 1 -1 -1
a 2 3+ 1 -1 1 1 -1 1 -1 1 1 -1
b2 4+ 1 -1 1 -1 1 1 -1 1 -1 1
eg 5+ 2 0 -2 0 0 2 0 -2 0 0
a tu I- I 1 1 1 1 -1 -1 -1 -1 -1
btu r 1 1 1 -1 -1 -1 -1 -1 1 1
a 2 3- 1 -1 1 1 -1 -1 1 -1 -1 1
b2 4- 1 -1 1 -1 1 -1 1 -1 1 -1
e. 5- 2 0 -2 0 0 -2 0 2 0 0
M E UxU, C 2z C 4z C 4; U 3i,UX ' I (JxUy Uz S4;S4z (JXyaXY
1+
2+ -i -1 -i -1
3+ -i -1 -i -1
4+ 1 -i -i 1 -i 1 -i 1
5+ 2 0 -2 0 0 2 0 -2 0 0
I- I 1 -1 -i -1 -i -1
2- 1 -i -1 -1 -i -1 1
r -i 1 -1 -1 -1 -i 1
4- 1 -i 1 -1 I -1 i -1 -1
5- 2 0 -2 0 0 -2 0 2 0 0
A E U, Ux Uz C 4v A, V E C 2z (Jx(Jy /T;;yUxy C 4z C 4;
y E Ux u, Uz al 1 1
bl 2 t -1 -t
1 t 1 b2 3 -t 1 -t
2 -t -1 a2 4 1 -I -t t
3 -t t -1 e 5 2 -2 0 0 0
4 -t -t 1 t = exp( - ipn) for direction A
t = exp( - ipn) t = i exp( - ipn) for direction V
Z,A E C 2z U 3i, UXY UiyUxy C 2v J:, S E Ux, (Iiy Uz
2 2 0 0 2 al 1 1
2 2 2 0 0 -2 a2 2 -1 -1 1
3 2 -2 2 -2 0 bl 3 -1 -1
4 2 -2 -2 2 0 a2 4 -1 -1
For the elements Ux, U" C 4z> C 4;, I, ux' u" S4;,
S4= the characters are zero in all the irreps. T E Ux u, U=
U E U, Ux U,
W E C 2z Ux uy
2 0 0 0
X E Uz C 2x C 2y C 2z I Ux u,
R E I C2x C 2y C 2z Ux U, Uz
1- 2 -2 0 0 0 0 0 0
2 1+ 2 2 0 0 0 0 0 0
no, 0, 0), M(l/2, 1/2,0), Z(O,O, 1/2), A(I/2, 1/2, 1/2), X(O, 1/2,0),
R(O, 1/2, 1/2), .1(0, p, 0), Yip, 1/2,0), A (0, 0, p), V(I/2, 1/2, p), T(p, 1/2, 1/2),
U(O, p, 1/2), W(O, 1/2, p), J:(p, p, 0), Sip, p, 1/2).
D(*k,a)[(IIO)]=(~ ~), (3.8.38)
where
A = d(k,a)[(Uxlv)] , B = d(k,a)[(Uylv)] ,
C = d(k,a)[(C 2z IO)], D = d(k,a)[(lIO)]
The form of full irrep matrices for the elements (O"zIO),(O"xlv), and (O"ylv)
is the same as C4v gE for the elements (C2zI0),(Uxlv),(Uylv) respectively.
Calculating the point group elements EgC 4z1 and C4v gE for g = C 4z ' C 4zt.
UXy,Uxy,O"xPO"xy,S4z,S4z1 one obtains, according to (3.8.14), all the other
matrices of the full group irreps D(*k,a)(g) which have zero diagonal blocks.
For symmetry lines 17,A,Ll inside a Brillouin zone the labels of small irreps
of little groups may be taken to be the same as for the corresponding wave vec-
tor point groups C 2v (17,Ll) and C4v (A). The Mulliken symbols for 17 and A are
also given in Table 3.14.
For the symmetry lines Y, T, U, W, Von the surface of a Brillouin zone the
small irreps of the little groups are connected with projective irreps of the point
group C2v (Table 3.14). Finally, for the symmetry line S on the surface of a
Brillouin zone all the fractional translations v are zero in the little group
elements (Rj IVj + an) so that the small irreps of the little groups are labeled by
indexes of irreps of the point group C2v '
The dimension of the full group irrep D(*k,a)(g) for the symmetry lines
is equal to nsna where ns is the number of rays in the star *k and na is the
small irrep dimension. For example, the irreps D(*A,5)(g) are four-dimensional
(two rays in the star *A with the wave vector point group C4v ; the small irrep
D(A,5) is two-dimensional). The irreps D(*T,l)(g), D(*U,l)(g), D(*W,l)(g) are eight-
dimensional (four rays in the stars with the wave vector point group C 2v , two
dimensional small irreps of the little group).
When obtaining the degeneracy of the energy levels in crystals it is neces-
sary to take into account not only the dimension of the full group irreps but also
Table 3.15. Compatibility relations for the space group D!:

r M 1+ 2+ 3+ 4+ 5+ I- T 3- 4- 5-
I: I: 2 2 3,4 4 3 3 4 1,2
L1 Y 4 4 2,3 2 2 3 3 1,4
A V 2 4 3 5 4 3 2 5
A Z 1 2 3 4 X 1 2 R 1+ I-
V A 1,3 2,4 5 5 L1 2,3 1,4 W 1 1

S S 1,3 2,4 2,3 1,4 Y 2,3 1,4 T 1 1
T V 1 1 1 1 W 1 1 V 1 1
possible additional degeneracy due to time inversion symmetry (Sect. 3.5.3).

Due to this symmetry (Sect. 5.3.6) two inequivalent (case 2) or two equivalent
(case 3) irreps of the wave vector group Ok stick together. In particular, this
sticking takes place for pairs of irreps Mt ,M:; Mj ,M4 ; Mi ,M:;; Mi ,M:;
(Table 3.14) so that at the M point of the Brillouin zone all the energy levels and
phonon frequencies are doubly degenerate. The time-inversion degeneracy oc-
curs also for small irreps Y1- Y4 and Y2 - Y3. Therefore the energy levels for
stars of k-points on the Y-line of the Brillouin zone are eight-fold degenerate
(four rays in the star and two pairs of sticking one-dimensional small irreps).
The compatibility relations of the space group Dl: are given in Table 3.15.
This table shows which irreps D(*kLoa)(g) of the group of kL for the symmetry line
occur in the representations D(ks.P)(g) of the group of Gk of the symmetry point
ks on this line when restricting D(*k.,a)(g) to elements of GkL . This table is calcu-
lated simply by using (2.2.28) and the characters of the small irreps of groups
Ok, Ok' The entries of the first rows of Table 3.15 give the intersection sym-
L s
metry point k of several symmetry lines in the Brillouin zone. The columns of
the table are labeled by irreps of the group Ok for that point. The entries in the
other rows of the first column give the symbols for the symmetry lines that inter-
sect in that point. The other columns then tell which irreps n(kva) occur in
the irreps n(ks'P) ~ Ok As an example let us consider the compatibility rela-
tions for the point ZL of the group n!'h:
(3.8.39)
4. Site Symmetry and Induced Representations
of Symmetry Groups
This chapter is most important for the group-theoretical foundations of the site-symmetry
approach. The concepts of a band as well as of the simple and composite induced representations of
space groups are discussed in detail. It also contains tables of simple induced representations for the
24 space groups.
4.1 Induced Representations of Point Groups. Correlation Tables
In Sect. 2.3 we have considered the procedures of subduction and induction of

reps of a finite group G. Let G be now one of the 32 point groups of a crystal.
Subducing the irreps of the group G with respect to its subgroup Hand
decomposing the subduced rep over the irreps of a subgroup one obtains a
correlation table. The rows of this table are labeled by irreps of a group G; the
columns denote different subgroups H of this group G. The frequencies of
subduction by each irrep of G for the irreps of these subgroups are listed in the
body of the table. One also has to take into account the possibility of different
orientations of isomorphic subgroups with respect to the group G.
As an example we consider the correlation table for the point group D Zh .
The point group DZh is an oriented site symmetry group of Wyckoff positions a
and b in the space group Dit (Sect. 3.4.2) and consists of8 elements: E, C Zz , U XY '
Uxy (rotations around three two-fold axes), I (inversion), (Jz, (J"y, (Jxy (reflections
in the planes perpendicular to the z, xy and xy directions). The subgroups of the
point subgroup DZh are D z , C Zv , C z , Cs ' C;. Different choices of two-fold axes
and reflection planes for groups C Zv , C z , Cs are possible. For example, three C Zv
subgroups are ClJ C Zz , (Jxy, (JXY)' C~~(U xy' (Jxy' (Jz), C~~(UXy, (Jxy, (Jz), which differ
by the choices of elements given in parentheses. The fragment of the correlation
table for the point group D~h (Table 4.1) gives the subduction frequencies r~l1.) for
different point subgroups CZV"
Using the Frobenius theorem one can also write the reciprocal correlation
table in which the irreps of the point group induced by irreps of its different
point subgroups are given. Representations of point groups induced by irreps of
their point subgroups Cnv , Cn (n = 2,3,4,6) and Cs are given in Table 4.2. The
latter subgroups may be considered as the site symmetry groups of atoms in
molecules and molecular clusters. The first column in each subtable of Table 4.2
contains the symbols of the point subgroup and its irreps. The rest of the
columns give the symbols of point groups and the induced representations de-
composed over the irreps of these groups. It is taken into account that the
induced reps are different for isomorphic subgroups of different orientations.
90 4. Site Symmetry and Induced Representations of Symmetry Groups
Table 4.1. Correlation table (fragment)

for the point group D;h
D;h cxy cx y
C2v 2v 2v
ag al al al
au a2 a2 a2
bIg a2 b2 b2
b lu al bl bl
b29 bl a2 bl
b2u b2 al b2
b3g b2 bl a2
b3u bl b2 al
Table 4.2. Induced representations of point groups
'r
I
C6v D6h C4v D4h Oh Cs) Yh Cs I

I Y C6 D6 C6h
I
I ,
al a lg a2 ",. al a lg a2" alge.t lu al : agtlu t 2u h g a : at l t2h a a l a2 aga.,
a2 a 2 ,a 1ll a 2 a29 a11.1 a1"eut 1g a2 : a u tlgt2ghu b bl b2 b.bu
bl b lg b2u bl bl.b2u a2.e.t2u el tlgh
: tlgtluggguhghu e 2): I,g' e\1) el e\~e\IJ
b2 b2.blu b2 b2.btu azueutZg e2 : t2gt2ugggu hghu e I): t 2gh e\2) el efie\2J
el e1ge lu e egeu t l.t2.t lut2u e ): t 2gh e~l) e2 e~~e~IJ
e2 e 2. e 2 u e(2) e e~2)e(2)
2u
C 3v D3h D3d r. 0. Yh C4 D4 0
al a~ai a 1g a 2 ., a l t2 al.a2ut2gtlu agtlu t 2ugggu hg a a l a2 0 1 et l

O2 a~a; a2g a h O2 t l a2g a lu t lg t 2u autlgt2gggYuhu b bl b2 a2et 2
e e'e" eyeu et I t2 ege.,t IUtZyt lutZu tlgtl u t2gt2ugggu 2hg2hu ell) e tl t2
e(2) e tl t2
C 2v D2d D2h D2h D2h D3h D4h D4h
al o l b2 ogb lu ogb2u o.b3u a~e' olgblgeu ol.b2geu

a2 O2 bl OUbig OUb2g Ou b3' a"Ie " Otublueg alub2ueg
bl e b2g b3u b3g blu b2.btu a~e" aZub2ueg aZUblue9
b2 e b3g b2u b lg b3u bl.b2u a;e' O2. b2geu O2. bl. eu
( (V)"x) (tTxtT z ) (tTytT z ) (tTytT z ) (tTXytTz )
(tTXytTXY ) (tTXytT z ) (tTXytTz )
C 2v D6h D6h T,. r. h Yh
01 atgbtue2gelu al.b2ue2.etu o.e.tu olet 2 OI.e.tlut2.t2u agf j u t2ugggu 2hghu

O2 Olu blg e lg e 2u Otu b2. e lg e 2u aue.,tg O2 et l Otu eut l. t 2. t 2u au t j gt2gggYuhg2 hu
bl O2u b2g e lg e 2u O2u blg e lg e 2u tgtU tl t2 O2u eut l. t tu t 2. tigtj u t2gt2uYgYu hghu
b2 a2.b2ue2gelU o2. b lu e2g e tu t.tu tl t2 O2. e t l. t lu t 2u tjgtj u t2gt2uYgguhghu
(tTxtTz ) (tTytT z ) (tTXytTz )
C3 D3 S6 C 3h T T,. 0 Y
0 a l o2 aga., a'a" ot o.out.tu Ol O2 t l t2 at l t22gh

e(1) e e~l)e~1) e'(1)e"(1) ell)t e~l)e~l)t.tu tj t 2g2h
etl t2
e (2 ) e e~2)e~2) e,(2)e,,(2) e (2 )t e~2)e~2)t.tu etl t2 tl t 2g2h
4.2 Induced Representations of Space Groups 91
Table4.2. (continued)
C2 84 C2h D2 D2 D2 D3 Dld D4 D4
a ab agau ab l ab2 ab3 ale alble a,ble a l b2e

b e b.b. b2b3 bl b3 bl b2 a 2e a 2b2e a 2b2e a 2b l e
(C2z ) (C2y ) (Clx ) (Ux ) (UXy )
C2 D3d D6 D6 T 0 Y
a algaluegeu a l b l e l e2 a l b2e l e 2 aet a l et l t 2t 2 at j t z2g3h

b aZgaZuegeu a 2b2e l e2 a 2bl e l e 2 tt a 2et l tl t2 2t j2tz2g2h
(Uy) (U.)
C, C2v C2v C2h C3v C3h C4v C4v
a' alb l a l b2 a.bu ale a'e' alble a,b2e

an a2b2 a2bl a.b. a 2e aile" a2b2e a2b l e
(ery) (erx ) (erx ) (er XY )
(ery) (er z)
(erXY ) (erz )
C, C4h C6v C6v C6h CSV
a' a.b.e. a l bl e l e 2 a l b2e l e2 agbue2gelu ajejeZ

an a.b.e. a 2b2e l e 2 a2b l e l e 2 a.b.e l.e2u aZe j eZ
(er.) (ery)
As an example one may compare the induced reps of the D2h group obtained
from irreps of isomorphic subgroups C 2v (C 2z , O"xy, O"XY)' C~~(U xY' O"xy, O"z) and
C~~(UXy, O"xy, O"z) (reflection planes contained in these groups are given in the last
rows of the corresponding subtables in Table 4.2). For example, b l (C2v)i D2h =
b2g + b 3u ; bl(C~~)iD2h = b3g + blu; bl (qDiD 2h = b2g + blu
Table 4.2, of induced reps, is a reciprocal correlation table of point groups
given in [4.1]. This table does not contain induced reps for subgroups Cs c
Cnv c G. To obtain the induced rep for these subgroups one has to induce twice:
from subgroup Cs to subgroup Cnv and then use Table 4.2 to induce from sub-
group Cnv to group G. For example: a'(Cs)iD 2d = a l (C 2v )iD 2d + b l (C 2v )iD 2d =
a l + b2 + e.
4.2 Induced Representations of Space Groups
Any subgroup rep generates some induced rep of a group (Sect. 2.3.3). In the
particular case of a space group G the small irreps of the little group G" c G
induce its full irreps D(*"a)(g) (Sect. 3.8.2).
In the next subsections we consider induced reps of space groups generated
by the irreps Pof the site symmetry subgroup Gil of point q in the direct lattice
space (PiG). This type of induced rep of space groups was considered in [4.2, 3].
In [4.4] a more general concept of band reps was introduced.
4.2.1 Induction from Site Symmetry Subgroups of Space Groups
As was seen in Sect. 3.3.1, all elements of the space group G can be written in the
form g = (Rlv + a.), where v is a fractional lattice translation associated with
the F point group element R and a" is a direct lattice translation vector.
The elements of the site symmetry group Gq c G of the point q in the direct
lattice space are those elements of G for which gqq = (Rqlvq + a.)q = q (Sect.
3.4.1). The site symmetry group G q is isomorphic with the point group Fq
formed by R q. Let the representatives gjn U = 1,2, ... , nq = np/no in the
decomposition q
(4.2.1)
be chosen so that the points
(4.2.2)
occupy the positions within the smallest unit cell (primitive or Wigner-Seitz).
The operations gj. generate from the point q sublattices qj + a. (j = 1,2, ... , nq).
Let the local functions Jt;<fl(r) == Jt;(r - q), i = 1, 2, ... , np be centered at
point q of the direct lattice and span the space of the irrep f3 of the site symmetry
group G q c G with matrices d(Pl(gq) and characters iP1(gq) (gq E G q). The na-
ture of these functions depends on the physical problem under consideration. In
the electron band theory of crystals Jt;(Pl(r - qA) are atomic functions of atom
A (Sect 5.4). In phonon spectroscopy applications Jt;(Pl(r - qA) mean the com-
ponents of atomic displacements of an atom A (Chap. 8). In magnetically
ordered crystals these functions are the magnetic moments of atoms (Chap. 9).
Functions Jt;<fl(r) transform as
gqJt;<fl(r) = Jt;(Pl(R;l (r - v, - a. - R'Iq
= Jt;(Pl(R;l (r - q
= L dW(R'I) Jt;!11(r)
i'=l
, (4.2.3)
since the vector q remains invariant under the operations of the site group G'I'
All the functions Jt;<fl(r) (i = 1,2, ... , np) are associated with the site q.
The local functions associated with the smallest unit cell are obtained from
local functions Jt;<fl(r) through
(4.2.4)
i=I,2, ... ,np , j = 1, ... , nq .
Functions in other unit cells are obtained through
W;Y)(r - an) = {Elan} W;Y)(r)

(4.2.5)
= W;(P)(R j- 1 (r - qj - an .
The local functions W;Y)(r - an) form the basis of an induced rep PiG of
space group G. Indeed, let the element (R Iv) E G transform the jth sublattice into
the j'th one and be written in the form
(4.2.6)
where R = Rj'RqR j- 1 (R q E FIJ) and the lattice vector ajj' = (Rlv)qj - qj" Equa-
tion (4.2.6) may be checked directly. From (4.2.6) we get for the local functions
W(fl)(r
'J
- an )
{Rlv} W;Y)(r - an) = L dW(Rj-;lRR)W;!1)(r - Ra. - aj'j) . (4.2.7)

i'
The dimension of the rep 13 i G is infinite for the model of an infinite crystal.
In a cyclic model, the infinite crystal is replaced by a main region consisting of
N smallest unit cells (Sect. 3.3.2) and periodic boundary conditions are intro-
duced. The total number of local functions W;}P)(r - a.) is finite and equals
npnlJN (i = 1, ... , np; j = 1, ... , n q; n takes N values). These functions form an
npnqN-dimensional space of the rep of the space group G. This rep matrix
consists of np x np blocks arising from diP) [See (4.2.7)].
To specify the induced rep PiG in the basis of local functions W;y)(r - a.)
(q-basis) one has to indicate the symmetry center q of local functions by its
Wyckoff position and the irrep 13 of the site symmetry point group GIJ' Thus, in
the q-basis the induced rep PiG is specified by the index (q,p).
4.2.2 Induced Representations in the k-Basis. Band Representations

In Sect. 3.8 we have considered the space groups irreps D(*/c'~)(g) defined by
stars *k of wave vectors k from the first Brillouin zone and by irreps (X of little
groups G/c. Let us construct in the space of induced rep (q, 13) new basis functions
that span the space of irreps of the translation group T (Bloch functions)
tfJW(k, r) = L exp(ik . an) W;y)(r - a.) (i = 1, ... , np;j = 1, ... , nq)

"
(4.2.8)
and vice versa

W;j(P) (r - V.
all ) -- (2n)3 f exp(-'.lk ./,(P) k
all)'/' d
ij ( , r) k , (4.2.9)
W;Y/)(r - all) = N- 1 L exp( - ik . a,,)t/J11)(k, r) (4.2.10)

"
for infinite and cyclic models of a crystal, respectively. Using (4.2.9, 10) and
(4.2.7) one obtains
(4.2.11)
Let the wave vector k be fixed and 9 = (Rlv) E G". Then p = npn, functions
t/J11)(k, r) span the space of the small representation of the little group G" with the
character
(4.2.12)
where
(4.2.13)
Knowing the characters (4.2.12) of the induced rep one can easily calculate the
number of times the small irrep D(k,y) of the group G k with characters
X(k'Y)(g), (gEGk ) is contained in the induced rep (q,p).
This procedure givel the labels of the induced rep (q, f3) in the k-basis
corresponding to those in the q-basis, i.e., the results of the reduction of the
induced rep over irreps of the group G". All the information obtained can be
specified by listing the symmetry (the labels of irreps) of the Bloch states with
wave vectors k corresponding only to a relatively small number of k-points in
the Brillouin zone forming a set K. The set K contains the inequivalent symme-
try points of the Brillouin zone and one representative point from each
inequivalent symmetry element (symmetry line or symmetry plane) if the latter
does not contain the points of higher symmetry.
The symmetry properties of basis functions with other k vectors can be
determined with the use of the compatibility relations (Sect. 3.8.6).
The set K for the space groups with high symmetry classes consists only of
the symmetry points. For instance, the set K for the space groups of the
crystallographic class D4h contains the points r, X, M, Z, R, A (Fig. 3.6). The
symmetry points can be absent in the Brillouin zone of space groups with low
symmetry classes. For example, three points r, X, M (as the representatives of
4.2 Induced Representations of Space Groups 9S
three symmetry lines rz, XR, MA) form the set K for the tetragonal space
groups of the class C 4v (Fig. 3.6).
The symmetry properties of basis functions of an induced rep are described
by the full group irreps (*k, y) or by the small irreps (k, y) of the wave vector
groups Gk unambiguously related to them. Thus, as an index of an induced rep
we shall use the symbols of those small irreps of the little groups G k with wave
vectors from the set K that correspond to basis functions of a given induced rep
(4.2.14)
The index of the induced rep (4.2.14) can also be considered as the set of
so-called subduction frequencies r~:i~~). The latter give the number of times the
irrep (*k, y) of G is contained in the induced rep (q, P). From the Frobenius
theorem the subduction frequencies r~:t.~) are equal to the number of times the
irrep (*k, y) subduces the irrep Pof Gq'
r(*k,y) - r(q,P) (4.2.15)

P - (*k,y)
= I (x(P)(g))*X(*k,Y)(g) , (4.2.16)
gEG.
where X<*k'Y)(g) and X<P)(g) are the characters of the irreps (*k, y) of G and Pof G q
respectively.
To calculate the subduction frequencies r~:i~~) one may use one of the fol-
lowing procedures. The first uses (4.2.12) and does not require knowing the full
irrep (*k, y) characters. Indeed one obtains, according to (4.2.12), the characters
x<f)(g) of the rep of a little group Gk' Reducing this rep requires the characters
of the irreps of the little group Gk tabulated in [4.5] and gives the induced rep
index (4.2.14) in the k-basis.
The second procedure for calculating subduction frequencies uses (4.2.16)
and requires the character X(*k,y) of full space group irreps. Usually the tables of
space group irreps contain the small irreps of little groups. Since the full space
group irreps are induced by small irreps of little groups (Sect. 3.8.2) their
characters can be calculated using the characters of the latter:
X(*kY)(g) = I i(gjl gg J (4.2.17)

j
where
(4.2.18)
and gj are representatives of the co sets in the decomposition
(4.2.19)
Knowing X(*kY)(g) one can easily find the frequencies r~k.Y) of subduction
(*ky)!G, which are equal, according to the Frobenius theorem, to intertwining
numbers r:!/~) of induction PiG.
This subduction procedure is very simple for those irreps (*ky) of G which
have one or few rays in the star *k. This condition is fulfilled as usual for the
wave vectors k E K. For instance, in the set K for space group Dlt [and for all
space groups of the same class D4h with a simple tetragonal lattice, i.e., for the
space groups D~h (i = 1,2, ... ,16)] there are four wave vectors (F, M, Z, A) with
one ray in the star and two wave vectors (X, R) with two rays in the star (Sect.
3.8.6). The subduction procedure is simplest for the irreps with one ray stars,
where full space group irreps coincide with the small ones of the little groups
and the frequencies in question are given directly by subduction of the small
irreps of the little groups.
The third way of induced rep generation uses Mackey's subgroup theorem
[4.6J
(4.2.20)
In (4.2.20) Ls = G, n G ks, D!kY)(gsg kg;1) = D(kY)(g k) is the irrep of the conjugate

group G ks = gsG k g;1. The space group elements gs E G (gs . Gk,gs . G,) are
double coset representatives in the double coset decomposition of G with re-
spect to G k and G,
(4.2.21)
For the right-hand side of (4.2.20) one may use the reciprocity theorem
subducing the irreps of Gf on the intersection Ls of the groups Gks and G,. Then
the frequency r fls of d(fJ) in (D}kY) !Ls)iG, is equal to
r fls = ni; L lk Y)(g;lggsHx(fJ)(g* (4.2.22)

geLs
where X(k y) and X(fl) are the irreps' characters for groups G k and G, respectively,
nL being the order of the group Ls. This approach appears to be very efficient
in Sthe cases when the intersection Ls of the groups G k and G, consists of a small
number of elements.
To calculate subduction frequencies (4.2.16) one makes the summation over
the elements 9 = (Rlv + aR ) of the q-site symmetry group Gil c G. The pure
translations a R are important in determining the characters X(*k.Y)(g): after

transforming the point q by the coset representative (RI v) the translation aR
brings the transformed point back to q. For certain transformations no addi-
tional translations aR are needed. These pure translations give the factor
exp( - ik . a R ) by which irreps' characters X(*k, Y)(R Iv) are multiplied to obtain
X(*k, Y)(g) in (4.2.16).
Comparing the considered ways of finding the induced rep index in the
k-basis one may conclude: 1. the first one is more appropriate for q-sets
consisting of only one Wyckoff position in the unit cell (this is possible only in
symmorphic space groups); 2. the second one is more appropriate for those
wave vector stars which consist of one ray so that the full and small irreps
coincide. In these cases the sums (4.2.12) and (4.2.17) contain only one term. In
Sect. 4.2.4 we illustrate both procedures of the induced rep generation for the
example of the Dlt space group.
In [4.4, 7-9] the concept of a band rep of a space group, which may be an
induced rep, was introduced. Band reps were used to define the symmetry of an
electron energy band as a whole entity [4.10]. Use of band reps in the electron
theory of crystalline solids is considered in Sect. 5.1. Here we only discuss the
connection between induced and band reps of a space group.
From the group-theoretical point of view a band rep of a space group is a
direct sum of its irreps which have the following properties:
1) the space of the band rep contains the basis vectors with all the k-vector
stars in the Brillouin zone;
2) the compatibility relations are fulfilled throughout the Brillouin zone.
H is obvious that at every k-point there is the same number p of Bloch-type
basis states.
In a cyclic model of a crystal with N primitive cells in the main region a
band rep is an Np-dimensional reducible rep of a space group. An induced rep
is a particular case of a band rep as it satisfies both properties 1 and 2 with
p = nqnp (np is the dimension of the site symmetry group irrep for a point q
belonging to the set of nq-points in the unit cell).
The index of a band rep in the k-basis has the form given by (4.2.14). By
analogy with the same index for an induced rep, all informaton about the band
rep can be given by specifying the symmetry (the labels of irreps) of the basis
vectors with wave vectors k E K.
It is seen now that band reps (induced reps included) of space groups can be
specified by the index (4.2.14) in the k-basis, and only those band reps which are
induced ones can also be specified in the q-basis in the form (q, /3).
4.2.3 Simple and Composite Induced Representations

The use of the q-basis of induced reps allows one to introduce the concept of
simple induced reps, which facilitates the analysis of all possible types of induced
reps for a given space group. An induced rep is called simple if it is impossible
to split up the space of this rep into subspaces which are invariant under opera-
tors {j (g E G) and are also the spaces of some induced reps.
By definition, a composite induced rep is a direct sum of the simple ones. As
a group rep, a simple induced rep is reducible, so we prefer to avoid the expres-
sion "irreducible induced rep" used in [4.4]. The term introduced in [4.10],
"elementary induced rep", is equivalent to the term "simple induced rep" used in
this book.
All simple induced reps may be generated by induction from the irreps of
site symmetry groups Gq' of a relatively small number of q' -points forming the
set Q in the Wigner-Seitz unit cell of the direct lattice. The set Q consists of
1) all the inequivalent symmetry points of the Wigner-Seitz unit cell;
2) one representative point from all the inequivalent symmetry lines and sym-
metry planes that do not contain the symmetry points.
The site groups G q for q E Q are called in [4.10] maximal isotropy sub-
groups. The set Q in the Wigner-Seitz unit cell is determined in the same way as
the set K in the Brillouin zone. However, the action of symmetry operations in
the direct and reciprocal spaces is different.
A reducible rep d(g) = Lp rpdIP)(g) of the site group Gq induces a composite
induced rep that is the direct sum of reps induced by the irreps dIP)(g) (g E Gq)'
Now let us show that if the q-point does not belong to the set Q, the rep
(q, 13) induced from the irrep 13 of the site group Gq is composite. Let q' be one of
the points in the set Q for which the site group Gq' contains Gq as a subgroup
(G q c Gq')' This condition may be satisfied for several points q' of the set Q. The
decomposition of the site group G" into left co sets with respect to the subgroup
Gq has the form
n
Gq , = L
j=l
(Rjlv)G q (4.2.23)
If the functions ~~)(r) (i = 1,2, ... , np) span the space of an irrep 13 of the group
Gq then nnp functions
(4.2.24)
form the space of the site group Gq , rep piGq , induced from the irrep P of its
subgroup Gq Let us decompose the rep piGq , into the irreps a' of the group Gq "
f3i Gq, = L ra,rx' . (4.2.25)

a'
The irrep 13 of the group Gq and rep f3iGq, of the group Gq, generate the same
induced rep
(q,f3) = (q',f3i Gq,) = L ra,(q',rx') , (4.2.26)

a'
which is obviously composite. Thus we have proved that all the possible simple
4.3 Double-Valued Induced Representations 99
induced reps of a given space group G may be generated by induction from the
irreps of the subgroups G q , for q' E Q.
In [4.10] a complete classification of the inequivalent simple induced reps is
given and all the cases when the reps induced from irreps of maximal isotropy
subgroups can be equivalent to one another are considered. First of all, equiva-
lent induced reps at the same site q' E Q arise [4.10]
1) by induction from one-dimensional irreps forming an orbit of the normal-
izer N G( G'I'); there are 23 pairs of them belonging to 15 space groups; and
2) four types of isotropy subgroups (C 2v , D 2 , D 2h , T) may generate reps in-
duced by irreps which do not form an orbit of N G( G'I')' There are 34 pairs
of them belonging to 25 space groups.
Second, there are 17 pairs of different maximal isotropy subgroups (be-
longing to 14 space groups) yielding 63 pairs of equivalent induced reps by
induction from one-dimensional irreps. When inducing from two-dimensional
irreps of isotropy subgroups, 33 pairs of equivalent induced reps are obtained,
belonging to 23 space groups. In total there are 153 pairs of equivalent induced
reps (57 at the same site and 96 at different sites) induced from different irreps of
maximal isotropy subgroups. In [4.10] it was also shown that 40 reps belonging
to 25 space groups and induced from irreps of maximal isotropy groups are
composite.
There is a formal analogy between simple induced reps and reps irreducible
in the usual group-theoretical sense. However, this analogy is not complete.
Indeed, the composite induced rep decomposition into simple ones is not always
unique. This occurs whenever the site symmetry group Gq is not the maximal
isotropy one (q : Q). In this case the group Gq is a subgroup of several maximal
isotropy groups G q , (q' E Q). Consequently, the induced rep decomposition
(4.2.26) will be different for different points q' E Q (G q C G q ,).
4.3 Double-Valued Induced Representations

The discussion of induced reps of a single space group G (given in Sect. 4.2) may
be directly extended to the double space group G using the coset decomposition
G= L [(R;lv;)T + (R;Elv;)TJ
;
, (4.3.1)
In (4.3.1) R;, R; = ER; are elements of the double point group F and T is the
translation subgroup of the space group G.
Let GIJ be a q-site symmetry group. The double point group GIJ consists of
both elements gq E Gq and 9'1 = gqE. The irreps of a double group G(GIJ) can be
divided into two types (Sect. 3.8.4), a and b. In the irreps D(Y)(d(a) of a-type, the
elements 9 and 9 are represented by the same matrix, so that the irreps D(Y)(d(a)
correspond to single-valued irreps of the group G (G 'I)' In the irreps D(Y)(d(ii) of
b-type, elements g and g are represented by matrices with opposite signs. The
b-type irreps are double-valued irreps ofthe group G (G,).
Let the space groups G and G be decomposed into cosets with respect to
their q-site symmetry subgroups,
(4.3.2)
In (4.3.2) the coset representatives gjll = (Rjl Vj + all) (j = 1, 2, ... , t; a" are the
translation vectors of the Bravais lattice) are chosen to be the same for the
groups G and G.
Let W;l (r) = W;(r - q) be the functions forming the basis of the irrep
d(~)(d(ii) of the group G,. The functions
I W;j(r - all) = gjlfW;l(r) I (4.3.3)
form the basis of the rep of the group G induced from the irreps d(~)(d(ii) of the
subgroup G, c G.
Acting on the local functions (4.3.3) by E and taking into account that
Eg jlf = gj"E one obtains the following results. The a-type irreps d(~) of the group
G, (single-valued irreps of G,) generate a-type induced reps of the group G (or
single-valued induced reps of the space group G). The single-valued induced
reps were considered in Sects. 4.2.1-3. In Chap. 5 we consider the application of
single-valued induced reps to analyze the symmetry of localized crystalline or-
bitals when relativistic effects are not included.
When the relativistic effects (spin-orbit coupling) are taken into account the
one-electron atomic wave functions transform according to the double-valued
reps of the site symmetry group G,. The irreps d(ii) (b-type irreps) of the group
G, (double-valued irreps of the group G,) generate b-type induced reps of the
double group G (double-valued induced reps of the space group G).
The description of the double-valued induced reps of space groups G may
be developed in the same way as that of single-valued induced reps. Any double-
valued induced rep is simple or composite. To generate all the possible simple
double-valued induced reps for a given space group G one has to consider only
those reps of the group G which are induced by double-valued irreps of the
q-site symmetry group Gf with q E Q. The set Q is defined in the same way as for
the single-valued induced reps (Sect. 4.2).
4.4 Generation of the Simple Induced Representations

of the Space Group D::
The space group D!: was described in Sect. 3.4.1. As is seen from Table 3.2, there
are eleven different types of Wyckoff positions for this group. The set Q includes
4.4 Generation of the Simple Induced Representations of the Space Group Dl: 101
only four of them: a(O, 0, 0), b(O,O, 1/2), c(O, 1/2,0), d(O, 1/2, 1/4). The site sym-
metry group of a, b positions is D2h , the site symmetry groups of c and d
positions are C 2h and S4' respectivey.
The irreps of space group Dit are considered in Sect. 3.8.6. As seen from
Table 3.14, in the Brillouin zone there are six symmetry points F(O 0 0),
M(I/2, 1/2,0), Z(O,O, 1/2), A(I/2, 1/2, 1/2), X(I/2, 0, 0), R(I/2, 0,1/2). These points
form the set K for space groups with a simple tetragonal lattice and crystal
point group F = D4h .
To generate the simple induced reps one takes into account that the stars
*T, *M, *Z, *A consist of only one ray. Therefore the small irreps (k, y) of little
groups Gk corresponding to these points coincide with the full irreps of space
group Dit. In this case the Frobenius theorem may be used to find the irreduc-
ible components of the induced reps (q, p): by subducing irreps at points T, M,
Z, A on site symmetry groups of Wyckoff positions a, b, c, d one obtains
subduction frequencies r~l:~l. This subduction procedure requires characters X(P)
of the site symmetry groups taken from Table 3.6 and the characters of small
irreps taken from [4.11]. The latter are multiplied by the factors exp( - ik . aR),
where a R = q - (Rlv)q are pure translations, (Sect. 4.2.2). In Table 4.3 these pure
translations for Wyckoff positions b, c, d are given (all these translations are zero
for the a-position since the latter is taken as the origin of the coordinate system)
expressed through the primitive translation vectors ai' a2 , a 3 of the simple
tetragonal lattice.
Simple induced rep generation for two-ray stars X, R may also be
performed by subducing the full irreps of the space group Dit. The characters
of these full irreps (4.2.17) may be found if one uses small irreps from the tables
[4.11] (see also Table 3.14) and the block-diagonal matrices of full irreps given
by Kovalev [4.12].
The second way of generating simple induced reps is connected with direct
calculation of the characters of induced reps for the elements of the little group
according to (4.2.12). The procedure does not depend on the number ofrays in
Table 4.3. The pure translations a R = q - (Rlv)q for the space group Dl:
and q-points of the set Q
Space group qb, qb, qc, qd,

element (Rlv) (1/2,1/2,0) (0,0,1/2) (0,1/2,0) (0, 1/2, 1/4)
(EIO) 0 0 0 0
(C2z IO) al + a2 0 a2 a2
(Ux,IO) 0 a3
(UxyIO) al + a2 a3
(IIO) al + a2 a3 a2
(azIO) 0 a3 0
(ax,IO) 0 0
(axyIO) al + a2 0
(S4zI1/2, 1/2, 1/2) 0
(Siz1 Il/2, 1/2, 1/2) -a l
Table 4.4. Generation of single-valued simple induced representations of the space group Dl:
(2-point of the Brillouin zone, Wyckoff position b)a
~ 2C4z C 2z 2Ux ~ !:!& I 2S4 ~ 2ux ~ ~ 2
2 0 2 0 0 0 0 0 0 0 2 2 I
2 0 2 0 0 0 0 0 0 0 -2 -2 2
2 0 -2 0 -2 2 0 0 0 0 0 0 3
2 0 -2 0 2 -2 0 0 0 0 0 0 4
a l1 (000) (ITO) (OOO)(ITO)(IIO) (000) (OOO)(IIO)

a 22 (000) (000) (001)(001)(001) (001) (000)(000)
exp( -ik' a l1 ) I I 1 I I I I I
exp( - ik a 22 ) I I -I -I -1 -1 1 1
a. 2 0 2 0 0 0 0 0 0 0 2 2 1
b1 2 0 2 0 0 0 0 0 0 0 -2 -2 2
b2 2 0 -2 0 -2 2 0 0 0 0 0 0 3
b3 2 0 -2 0 2 -2 0 0 0 0 0 0 4
a. 2 0 2 0 0 0 0 0 0 0 -2 -2 2
b1 2 0 2 0 0 0 0 0 0 0 2 2 I
b2 2 0 -2 0 -2 2 0 0 0 0 0 0 3
b3 2 0 -2 0 2 -2 0 0 0 0 0 0 4
a Pure translations a ii (j = 1,2) are given in units of primitive translations aI' a 2 , a 3 of a simple
tegragonallattice. For example all = (IIO) means that all = - a , - a2'
Table 4.5. Simple induced representations of the Dl: space group
q p r M 2 A X R
a b
a a. 1+4+ 1+4+ 1 1 2 1+ 1-
a. 1-4- 1-4- 2 2 I 1- 1+
b b1 2+3+ 2+3+ 2 2 2 1+ 1-
b1 rr rr I I I 1- 1+
b2 5+ 5+ 3 3 I 1+ 1-
b2 5- 5- 3 3 2 1- 1+
b3 5+ 5+ 4 4 I 1+ 1-
b3 5- 5- 4 4 2 1- 1+
a. 1+2+3+4+ 5-5- 12 34 22 1+1-

c a. l-rr4- 5+5+ 12 34 11 1+1-
b. 5+5+ l-r3-4- 34 12 11 1+1-
b. 5-5- 1+2+3+4+ 34 12 22 1+1-
d a l+r3+4- 5+5- 12 34 12 1+1-

b 1-2+r4+ 5+5- 12 34 12 1+1-
e(1) 5+5- 1+2-3+4- 34 12 12 1+1-
e(2) 5+5- 1-2+r4+ 34 12 12 1+1-
In (aac) units: a(I00), a 2 (010), a3(001)

Q: D2h (m.mm) - a(OOO), b(I/2, 1/2,0);
C2h (2/m .. ) - c(I/2,0,0); S4(4 .. ) - d(O, 1/2, 1/4);
In units of (2rr./a,2rr./a,2rr./c): b 1 (100), b2 (01O), b3(001);
K: D4h - T(OOO), M(I/2, 1/2,0),2(0,0,1/2), A(I/2, 1/2, 1/2);
D2h - X(I/2, 0, 0), R(I/2,0, 1/2).
4.5 The Twenty-Four Most Common Space Groups 103
wave vector stars. We illustrate this procedure by calculating the k-basis sym-
bols of induced reps of the space group D!t for the Z-point of the Brillouin
zone and the Wyckoff position b. In the first row of Table 4.4 the coset
representatives of the little group G z are given [for brevity only the operations
R of elements of point group Fz are given, the translational parts correspond
to (3.4.1)]. The characters of four two-dimensional small irreps ZI,Z2,Z3,Z4
are taken from [4.11] (Table 3.14) and given in the next four rows of Table 4.4.
These are connected with the projective irreps of the point group D4h of the
wave vector Z. Note that the elements UXY ' UXY have different characters in
these small irreps. The Wyckoff position b consists of two points qb 1
(112,112,0) and qb2 (0,0,112) with site symmetry group DZh (the elements of
this group are given in the first column of Table 4.3). In Table 4.4 the elements
of the DZh point group are underlined. The characters of the other eight
elements R $DZh are zero in the induced rep; they are listed in the last
eight rows of Table 4.4. The point group F z = DZh may be written as
F z = D Zh + UxD Zh . The operation (Ux ll12, 112, 112) transforms the second of
two b-points into the first one. If R j = E, Ux and REUx D 2h then R j-l R Rj$DZh
and the character of the element (R Iv) is zero at the small reps of the little
group Gz under consideration (see Sect. 4.2.13). They are listed in the last
eight rows of Table 4.4. If R j = E, Ux and REDzh then R j-l RRj ED2h .
Calculating, in units of the primitive translations aj, a2, a3, the pure transla-
tions ajj= (Rlv)qb-qb(REDzh,j= 1,2)one finds the factors exp(-ikall),
exp ( - ikaz2) give~ in table 4.4 for the Z-point of the Brillouin zone. Using
(4.2.12, 13) and tables of the characters of the DZh point group one obtains
the characters of the underlined elements in Table 4.4. Thus the last eight rows
of Table 4.4 contain the characters of the induced reps calculated for the Z-
point of the Brillouin zone. In the case considered they appear to be irreduci-
ble. Comparing the characters of induced reps with those given in rows 2 - 5
of Table 4.4 one obtains the indexes of induced reps for the Z wave vector
given in the last column.
In Table 4.5 single-valued simple induced reps of the D!t space group are
given, generated by the two described procedures.
To generate double-valued simple induced reps both procedures may be
applied. However, the characters of double-valued irreps of both the point and .
space groups must be used in the calculations.
4.5 The Twenty-Four Most Common Space Groups: Crystal

Structures and Tables of Simple Induced Representations
4.5.1 Tables of Simple Induced Representations and Their Use

The correspondence between symbols of simple induced reps in q- and k-bases
for q E Q and k E K is usually given in tables of simple induced reps having the
following structure (e.g., Table 4.5 for the D!t space group). The first two
columns of the table contain the labels of the induced reps in the q-basis (these
labels number the rows of the table): the international symbols (Roman letters
a, b, c and so on) of the Wyckoff positions (sites in direct space) and the
Mulliken symbols of the irreps of the site symmetry groups for these Wyckoff
positions. For example, (a, b3u ) and (b, b3u ) are the labels of induced reps in
q-basis for space group D!t (Table 4.5). The remaining columns give the labels
of induced reps in the k-basis, with the symbols of k-points (wave vectors) in the
first row of the table and the indexes of small irreps of little groups in subse-
quent rows. For example, 1+ in the column r means small irrep rt. Below the
table supplementary information is given-the primitive translations, the coor-
dinates and site symmetry groups of Wyckoff positions q E Q in the direct lattice
and the analogous data for the reciprocal lattice.
In this table of simple induced reps and in all the following ones the labeling
of the space group irreps is that of Miller and Love [4.11], the labeling of the
point group irreps is that of Bradley and Cracknell [4.13] and the site points q
are indexed as Wyckoff positions from the International Tables for Crystallog-
raphy [4.14].
According to the theory developed in Sect. 4.2, all the information about the
induced reps of a given space group is contained in the table of its simple
induced reps. Using these tables one can solve the following two purely mathe-
matical problems:
1) Finding the irreducible components of the space group reps induced by the
irreps of all the possible site symmetry subgroups for a given space group.
2) Finding the irreducible components of the site symmetry group reps
subduced by the irreps of the corresponding space group.
To solve these two problems one also needs
a) the compatibility relation tables for the irreps of space groups (Sect. 3.8.6);
b) Table 4.2 of induced reps of crystallographic point groups (Sect. 4.1).
We consider now in more detail the application of the tables of simple
induced reps for the solution of the two problems mentioned above. Suppose
one needs to find, for a given space group, the irreducible components of the
space group reps induced by some irrep of the site symmetry subgroup Gf' One
has to consider four cases.
la) q E Q and k E K. All the irreps in question can be found immediately from
the table of simple induced reps. For example, all the irreps (*k, /3) of the
space group D!t with k E K contained in the simple induced rep (a, ag ) are
enumerated in the row (a, ag ) of Table 4.5.
1b) q E Q and k K. After using the table of simple induced reps it is necessary
to use the table of compatibility relations. For example, the simple induced
rep (a, b2g ) of the group D!t contains the irrep rs+ (k E K) and, according to
Table 3.15 of compatibility relations, the irreps L1 2 , L13 with k K, since
rs+ !G A = L12 + L1 3
lc) q Q and k E K. First, Table 4.2 is necessary to obtain the decomposition

(4.2.25) and then the table of simple induced reps may be used. For example,
let us obtain the irreducible components with k E K for the induced rep
(f, a 1 )(f Q), i.e., q = f(x, x, 0) (Gf = C 2v (u XY ' uJ) and p = a 1 From Table
4.2 we obtain (f,ad = (a,a g ) + (a,b 3 J (Ga = D2h ) and then find in the rows
(a, ag ) and (a, b 3 J of Table 4.5 the irreps of the group Dlt with k E K con-
s,
tained in the induced rep (j,a 1 ): rt, r 4+, r s-, Mt, Mt, M and so on for
other k-points.
Id) q Q and k K. All three Tables 4.5,3.15, and 4.2 are necessary. For exam-
ple, the induced rep (f, a 1) of the Dlt group contains rt, r 4+, r s- (r E K) as
we have seen in lc and therefore 2,11,2,14 (,1 K) according to Table 3.15
(rt !GLf = L1 b r 4+ !GLf = L1 4 ,rs- !GLf = ,11 + ,14)'
If we now seek the irreducible components of the site symmetry group
reps subduced by a given space group irrep (*k, y) (problem 2) we also have four
cases to consider.
2a) k E K and q E Q. One finds the irrep (*k, y) in question in the rows of the
table of simple induced reps corresponding to the irreps of the site group
G1/' According to the Frobenius reciprocity theorem the irrep Pis contained
in the reducible rep of the group G1/ subduced by the irrep (*k, y) of the
space group G as many times as the symbol (*ky) is repeated in the
corresponding row of the table of simple induced reps. For example, the rep
of the site group Gb = D2h subduced by the irrep Z 1 of the space group Dlt
consists of the irreps ag and b 1u (Table 4.5): ZdG b = ag + b 1u '
2b) k E K and q Q. First one finds the irreps a' contained in the decomposi-
tion of the rep of the group G1/' (G f c Gf') subduced by the irrep (*ky) (as is
done in 2a). Then, using Table 4.2 one decomposes the reps of the group
GI/ subduced by the irreps a' of the group Gf ,. For example, the rep of
the group Gf = C 2v (u xy , uz ) subduced by the rep Z 1 of the space group
Dlt consists of the irreps a 1 and b1 since subducing the reps ag and b 1u of
the group Ga = D2h by the group Gf = C2V(Uxy,uz) gives the irreps a 1 and
b 1 (Table 4.2): ZI(DltHGf = (ZI(DltHGa HGf = (ag + blu)(D2hHC2v =
a1 + b1
2c) k K and q E Q. Using the compatibility relations table one completes the
simple induced reps table by one additional column only in the rows
corresponding to the irreps of the group Gf' Then one proceeds as in case
2a. For instance, according to Table 3.15 for the group Dlt: ZI!G A = Al +
A 3 , Z2!G A = A2 + A 4, Z3!G A = As, Z4!G A = As. Hence, subducing the
rep As(Ad by the group Ga = D2h one obtains the irreps As!Ga = b2g +
b39 + b2u + b 3u (AdGa = ag + b 1u )'
2d) k K and q Q. The irreducible components of the subduced rep can be
found in two steps: first the compatibility relations table is used as in case
2c and then Table 4.2 as in case 2b. For example, subducing the rep Al of
the group Dlt by the group Gf = C 2v gives the irreps a 1 and b 1 of the latter:
AdGf = a 1 + b 1
In this chapter the tables of simple induced reps of 25 frequently used space
groups (including space group D liz) are provided. The number of crystalline
compounds with known space groups is now over 20000 [4.15]. The six volume
compilation Crystal Structures by Wyckoff [4.15J and the Crystal Data Determi-
nation Tables by Donnay and Ondik [4.16J contain extensive information about
the structure of both inorganic and organic compounds. The space groups,
Bravais lattices, crystal classes and systems of crystalline substances are ana-
lyzed in [4.17]. In the following sections we give concise information about
some crystal structures with the space groups considered above.
4.5.2 Space Groups and Crystal Structures with Cubic Lattices

Simple induced reps for space groups with cubic lattices are given in Tables
4.6 - 12. Three types of cubic lattices are considered: simple cubic (space group
Ok, T~), face-centered cubic (space group ot
Oh, TJ) and body-centered
cubic (space groups Th). ot
Table 4.6. Simple induced representations of the Ol - Pm 3m space group
q f3 r R M X
a b a b a b
a lg 1+ 1+ 2- 1+ 4+ 1+ r
a lu I- I- 2+ 1- 4- 1- 3+
a Zg 2+ 2+ 1- 2+ 3+ 2+ 4-
a az r 2- 1+ 2- 3- r 4+
eg 3+ 3+ r 1+2+ 3+4+ 1+2+ r4-
b eu r r 3+ l-r r4- l-r 3+4+
t lg 4+ 4+ S- 3+S+ 2+S+ 3+S+ I-S-
t lu 4- 4- S+ rs- 2-S- rs- I+S+
t Zg S+ S+ 4- 4+S+ 1+S+ 4+S+ 2-S-
t zu S- S- 4+ 4-S- 1- S- 4-S- 2+S+
c d c d c d
a lg 1+3+ S+ 4- 4+S- 1+S- l+r4- 1+2+3-

a lu l-r S- 4+ 4-S+ I-S+ 1-3+4+ l-r3+
big 2+3+ 4+ S- 3+S- 2+S- 2+r4- 1+2+4-
c b lu rr 4- S+ 3-S+ 2-S+ r3+4+ rr4+
a Zg 4+ 2+3+ 1-3- 2+r4- l-r3+ 3+S- I-S+
d a zu 4- 2-3- 1+3+ r3+4+ 1+2+r rs+ I+S-
bzg S+ 1+3+ rr 1+3- 4- 1-2-4+ 4+S- rs+
b2u S- 1-3- 2+3+ 1-3+4+ 1+2+ 4- 4-S+ 2+S-
eg 4+S+ 4+S+ 4-S- l-rS+S- r4-S+S- 1-2- S+ S- 3+4+S+S-
e. 4-S- 4-S- 4+S+ 1+2+S+S- 3+4+S+S- 1+2+S+S- 3-4-S-S+
In (aaa) units: Q I (100), Qz(01O), Q3(001)

Q: Oh(m3m) - a(OOO), b(I/2, 1/2, 1/2);
D4h (4/mmm) - c(I/2, 1/2,0), d(I/2, 0, 0).
In (2n/a, 2n/a, 2n/a) units: b l (100), b z(01O), b 3(001);
K: Oh - T(OOO), R(I/2, 1/2, 1/2); D4h - M(I/2, 1/2,0), X(I/2, 0, 0)
Table 4.7. Simple induced representations of the 0: - Fm3m space group

q p r L X W
a b a b
a'g 1+ 1+ r 1+ 1 2
a,u I- I- 2+ 1- 4 3
a 2g 2+ 2+ 1- 2+ 2 1
a a 2u r r 1+ r 3 4
eg 3+ 3+ r 1+2+ 1 2 1 2
b eu r r 3+ l-r 3 4 3 4
t,. 4+ 2+3+ rr 3+5+ 3 5 4 5
t 'u 4- 2-r 1+3+ r5- 2 5 1 5
t2 5+ 1+3+ rr 4+5+ 4 5 3 5
t 2u 5- l-r 2+3+ 4-5- 1 5 2 5
c a, l+r l+r 4+r 5

a2 2+1- 2+1- 3+4- 5
e 3+r 3+r 3+4+3-4- 5 5
t, 4+5- 2+3+1-r 2+5+1-5- 1 2 3 4 5
t2 5+4- 1+3+2-3- 1+5+2-5- 1 2 3 4 5
d ag 1+ 3+ 5+ 1+3+2-r 1+4+r4-5- 125 5

au l-r5- 2+3+1-r 3+4+5+1-4- 345 5
b,g 2+3+4+ 2+3+1-r 2+3+r4-5- 1 255
b,u rr4- 1+3+rr 3+4+5+2-r 345 5
b29 4+5+ 1+3+1-r l-r5+5- 1 344 5
b2u 4-5- 1+3+1-r 1+2+5+5- 1 124 5
b39 4+5+ 2+3+rr 5+1-r5- 2 3 345
b3u 4-5- 2+3+rr 1+2+5+5- 1 223 5
In (aaa) units: a, (0,1/2,1/2), a 2(1/2, 0,1/2), a 3(1/2, 1/2,0).

Q: Oh(m3m) - a(OOO), b(I/2, 1/2, -1/2);
T.(43m) - c(I/4, 1/4, 1/4); D2h (mmm) - d(I/2, 0, 0).
In (21T./a, 21T./a, 21T./a) units: b, ( -111), b2 (1-11), b 3 (11-1).
K: Oh - T(OOO); D4h - X(O, 1/2,1/2);
D3d - L(I/2, 1/2, 1/2); Dzr W(I/4, 1/2,3/4).
Some crystal structures with cubic lattices are given below in the following
notations: space group symbol and (in brackets) Wyckoff position symbol, site
symmetry group of this position in crystal occupied by atoms (in parentheses).
Simple cubic lattice:
O~ [aOh(CS), bOh(Cl)]-cesium chloride
O~ [aOh(Ti), bOh(Ca), dD 4h(O)]-perovskite CaTi0 3
r,,6[aS6(Fe), cC 3 (S)]-pyrite FeS 2
Face-centered cubic lattice:
oZ [aOh(Cu)]-copper
Table 4.8. Simple induced representations of the Ol - F d3m space group
q p r X L W
a b
al 1+2- 1 l+r 1 2
a a2 1-2+ 2 1-2+ 2 1
e 3+r I 2 3+r 1 2 1 2
b tl 4+5- 234 1-2+3+r 1 1 2 122
t2 4-5+ 1 3 4 l+r3+r 1 2 2 112
c d
al 1+5+ 1 3 1+2-3- 1+2- 3+ 1 2

c a lu I-5- 2 3 1-2+ 3+ 1-2+r 1 2
a 2 2+4+ 2 4 1-2+3- r2+3+ 1 2
d a 2 r4- 1 4 l+r3+ l+rr 1 2
e. 3+4+5+ 1 234 l-r3+rr 1+2+3+3+3- 1 122
e. r4-5- 1 234 1+2+3+3+3- l-r3+r3- 1 122
For the direct and reciprocal lattice translation vectors and coordinates of K-set points see
Table 4.7.
Q: 7d(43m) - a(OOO), b(I/2, 1/2, -112);
D3d (.3m) - c(I/8, 1/8, 1/8), d( - 3/8, - 3/8, 5/8).
O~ [aOh(Na), bOh(CI)]-sodium chloride NaCI
O~ [aOh(Ca), c'T.!(F)]-fluorite CaFz
O~ [aTAC)]-diamond
O~ [a'T.!(Si), cD 3 AO)]-j1-cristobalite form of SiOz
O~ [a'T.!(Mg), dD 3 AAI), eC 3v (O)]-spinel AlzMg04
'T.!z [a'T.!(Zn), c'T.!(S)]-sphalerite ZnS
Body-centered cubic lattice:
OnaOh(W)]-tungsten
r,nbS 6 ,dC z(TI),eC 1 (O)]-thallium oxide Tl z0 3

Table 4.9. Simple induced representations of the O~ - Im3m space group
q p r H P N
a a, 1+ 1+ 1 1+
a lu I- I- 2 1-
a 2g 2+ 2+ 2 2+
a 2 r 2- 1 2-
eg 3+ 3+ 3 1+2+
e. r r 3 1-2-
t Ig 4+ 4+ 5 2+3+4+
tl. 4- 4- 4 2-r4-
t 2 5+ 5+ 4 1+3+4+
t 2 5- 5- 5 l-r4-
b a 'g 1+3+ 1+3+ 4 l+r4-

a, I-r I-r 5 1-3+4+
a 2g 4+ 4+ 2 3 1-2+2-
a 2 4- 4- 1 3 1+2+r
b 1g 2+3+ 2+3+ 5 2+r4-
b 1u 2-3- 2-r 4 2-3+4+
b29 5+ 5+ 1 3 1+1-2-
b2 5- 5- 2 3 1+1-2+
eg 4+5+ 4+5+ 4 5 l-r3+r4+4-
e. 4-5- 4-5- 4 5 1+2+3+r4+4-
c a lg 1+5+ r4- 1 4 1+2-3+r

a lu 1- 5- 2+4+ 2 5 1-2+3+r
a 2g 2+4+ 1- 5- 2 5 1-2+4+4-
a 2 r4- 1+5+ 14 1+2-4+4-
eg 3+4+5+ 3-4-5- 345 1+1-2+2-3+3-4+4-
e. r4-5- 3+4+5+ 345 1+1-2+r3+r4+4-
d al 1+3+5- 2+3+4- 4 5 1+2+3+3-3-4-

a2 rr4+ l-r5+ 4 5 1-2-3+4+4+4-
bl l-r5+ rr4+ 4 5 1-2-3+3+r4+
b2 2+3+4- 1+3+ 5- 4 5 1+2+r4+4-4-
e 4+4-5+5- 4+4-5+5- 123 345 1+1+1-1-2+2+2-2-3+3-4+4-
In (aaa) units:
U I (-1/2,1/2,1/2), u 2 (1/2, -1/2,1/2), u 3 (1/2, 1/2, -1/2)
Q: Oh(m3m) - a(OOO); D4h (4/mmm) - b(O, 1/2, 1/2);
D 3d (.3m) - c(l/2, 1/2, 1/2); D2cJ{4m2) - d(l/4, 1/2,3/4).
In (27t/a, 27t/a, 27t/a) units: b, (011), b 2 (101), b 3 (11O).
K: Oh - r(OOO); H( -1/2,1/2,1/2);
1d - P(I/4, 1/4, 1/4); D2h - N(O,O, 1/2).
Table 4.10. Simple induced representations of

the Ti - F43m space group
q p r X W
a b
al 1 1 1 2
a a2 2 2 2 1
e 3 1 2 1 2 1 2
b tl 5 4 5 134 234
t2 4 3 5 234 134
c d
al 1 3 3 4
c a2 2 4 4 3
e 3 3 4 3 4 3 4
d tI 5 2 5 1 2 3 1 2 4
t2 4 1 5 1 2 4 1 2 3
For the direct and reciprocal lattice

translation vectors see Table 4.7.
Q: 1d(43m) - a(OOO), b(I/2, 1/2, -1/2),
c(I/4, 1/4, 1/4), d( -1/4, -1/4, -1/4).
K: 1d - r(OOO); D2d- X(O, 1/2, 1/2);
S4 - W(I/4, 1/2, 3/4).
Table 4.11. Simple induced representations of the

1/,6 - Pa3 space group
q p r R M X
a b
ag 1+4+ 1+3+ l-r 1 2 1 2
a a. 1-4- I-r 1+3+ 1 2 1 2
e(l) 2+4+ 1+2+ 1-2- 1 2 1 2
9
b e~1) 2-4- 1-2- 1+2+ 1 2 1 2
e(2) 3+4+ 2+3+ 2-r 1 2 1 2
9
e~2) r4- rr 2+3+ 1 2 1 2
For the direct and reciprocal lattice translation vectors see

Table 4.6.
Q: C3i (.3.) - a(OOO), b (112, 112, 1/2).
K: Th - r (000); R (112, 112, 112); D2h - M(1I2, 1/2, 0);
X(1I2, 0, 0).
Table 4.12. Simple induced representations of the 1/,7 -la3 space group
q p r H P N
a b
a. 1+4+ 1+4+ 1-4- I 3 1 1
a au 1-4- 1-4- 1+4+ 1 3 1 1
2+4+ 2+4+ r4- 1 2 1 1

e(1)
b e~1) 2-4- r4- 2+4+ 1 2 1 1

3+4+ 3+4+ r4- 2 3 1 1

e(2)
e~2) 3-4- r4- 3+4+ 2 3 1 1
d a 1+1-2+2- 4+4+4-4- 112233 1 1 1

3+r4+4- 1 1 1
b 4+4+4-4- 1+1-2+2- 112233 1 1 1
3+r4+4- 1 1 1
For the direct and reciprocal lattice translation vectors see Table 4.9.
Q: C3i (.3.) - a(OOO), b(l/2, 1/2, 1/2); C2 (2 .. ) - d(l/4 + x, x, 1/4).
K: 1/, - r(OOO), H(I/2, 1/2, 1/2); T - P{1/4, 1/4, 1/4);
C2h - N(O,O, 1/2).
4.5.3 Space Groups and Crystal Structures with Hexagonal

and Trigonal Lattices
Simple induced reps for the space groups D~h' C~v' Dj, D~d with a hexagonal
Bravais lattice are given in Tables 4.13-16, respectively.
Some examples of crystal structures with a hexagonal lattice are the
following:
D~h[cD3h(Mg)]-magnesium
D~h[aD3ANi), cD 3h (As)]-nickel arsenide NiAs
D~h[bD3h,fC3v(Na), cD 3h (As)]-sodium arsenide Na 3 As
C~v[aC3v' bC 3v (C)]-graphite
C~v[bC3v(Zn, S)]-zinc sulfide ZnS, wurtzite structure
Dj[aC 2 (Si),cC 1 (0)]-silicondioxide Si0 2 , <x-quartz structure
Dj[aC 2 (Se)]-selenium
D~d[aD3ACd),dC3v(I)]-cadmium iodide CdI 2
D~d[aD3AO), dC 3v (0, La)]-lanthanum oxide La 2 0 3 structure
Simple induced reps for the D~d space group with a trigonal (rhombohedral)
Table 4.13. Simple induced representations of the Dth - P6 3 /mmc space group
q p r A K H M L
a a lg 1+4+ I I 2 3 1+3+ I
al 1-4- 2 I 2 3 1-3- 2
a2g 2+3+ 2 34 3 2+4+ 2
a2 rr I 3 4 3 r4- I
eg 5+6+ 3 5 6 I 2 1+2+3+4+ I 2
e. 5-6- 3 5 6 I 2 1-2-r4- I 2
b c, d b c d
b a; I+r I 1 4 5 3 I 2 1+4- 1
c a'{ 1-3+ 2 2 3 6 3 2 1 1-4+ 2
d a; 2+4- 2 I 4 5 3 I 2 2+r 2
a~ 2-4+ I 2 3 6 3 2 I r3+ I
e' 5+6- 3 5 5 145 1 2 2 3 1 3 1+2+r4- 1 2
e" 5-6+ 3 6 6 2 3 6 I 2 I 3 2 3 1-2-3+4+ 1 2
g ag 1+4+5+6+ I 3 125 6 123 I+I-r3+r4- I I 2

a. 1-4-5-6- 2 3 I 256 123 1+1-2+3+r4+ 1 2 2
bg 2+3+5+6+ 2 3 3 4 5 6 123 1-2+rr4+4- I 2 2
b. 2-rS-6- I 3 3 4 S6 123 1+2+2-3+4+4- 1 I 2
In (aac) units (hexagonal axes): a l (100), a2(OIO), a 3 (001)

Q: D3d (3m.) - a(OOO),
D3h (6m2) - b(O, 0,1/4), c(I/3, 2/3,1/4), d(I/3, 2/3, 3/4),
c2h ( .2/m.) - g(I/2, 0, 0).
In (2n/a, 2n/a, 2n/c) units (hexagonal axes): b l (100), b2 (01O), b3 (OOI).
K: D6h - T(OOO), A(O,O, 1/2); D3h - K( -1/3,2/3,0), H( -1/3,2/3,1/2);
D2h - M(t, 0, 0), L(t,O,t)

ctv - P6 3 mc space group
q p r K M
a b
a al I 4 I 2 3 I 4
b a2 2 3 1 2 3 2 3
e S6 3 3 1 2 3 I 234
The direct and reciprocal hexagonal lattice

translation vectors are given in Table 4.13.
Q: C3v (3m.) - a(OOz), b(I/3, 2/3, z).
K: C6v - T(OOO); C3v - K ( - 1/3, 2/3, 0);
C 2v - M(I/2, 0, 0).

Dj - P3 t 21 space group
q p r A K H
a b a b
a a I 3 I 3 2 3 1 3 I 3 2 3
b b 2 3 2 3 1 3 2 3 2 3 1 3
The direct and reciprocal hexagonal lattice translation

vectors are given in Table 4.13.
Q: C 2(.2.) - a(xxO), b(x, x, 1/2).
K: D3 - T(OOO), A(O,O, 1/2), K( -1/3,2/3,0),
H( -1/3, 2/3,1/2).
Table 4.16. Simple induced representations of the Djd - P3iiil space group
q p r A K H M L
a b a b a b
atg 1+ 1+ r I I 2 1+ 1+ 2-
a a tu I- I- 2+ 1 I 2 I- I- 2+
a 2g 2+ 2+ 1- 2 2 I 2+ 2+ 1-
b a 2u 2- r 1+ 2 2 1 r 2- 1+
eg 3+ 3+ r 3 3 3 1+2+ 1+2+ 1-2-
eu 3- 3- 3+ 3 3 3 1-r 1-r 1+2+
d at I+r 1+2- 3 3 1+2- 1+2-

a2 1-2+ 1-2+ 3 3 1-2+ 1-2+
e 3+r 3+r 1 2 3 123 1+1-2+2- 1+1-2+2-
e f e f e f
e ag 1+3+ 1+3+ rr 1 3 1 3 2 3 1+1-r 1+I-r 1+2+r

au 1-r I-r 2+3+ I 3 I 3 2 3 1+1-2+ I+I-r 1+2+r
f bg 2+3+ 2+3+ I-r 2 3 2 3 1 3 1-2+r 1-2+r 1+1-2+
bu rr rr 1+3+ 2 3 2 3 1 3 1+2+2- 1+2+2- 1+1-2-
The direct and reciprocal hexagonal lattice translation vectors are given in Table 4.13.
Q: D3d(3m.) - a(OOO), b(O,O, 1/2); C3v (3m.) - d(1/3, 2/3, z);
C2h (.2/m.) - e(1/2, 0, 0), f(1/2, 0,1/2);
K: D3d - T(OOO), A(O, 0,1/2); D3 - K( -1/3, 2/3, 0),
H( -1/3, 2/3,1/2); C2h - M(1/2, 0, 0), L(1/2, 0,1/2).
Bravais lattice are given in Table 4.17. Some examples of structures with the
symmetry of this space group are
D~d[cC3(AI),eC2(O)]-corundum Al 20 3 structure
D~d[aD3(C)' bS 6 (Ca), eC 2(O)]-calcite CaC0 3 structure
D~d[aD3(La), bS 6 (Cu), eC2(O)]-LaCu03 structure.

Table 4.17. Simple induced representations of the D~d - R3c space

group
q fJ r Z L F
a al 1+1- 3 1 1+1-
a2 2+r 3 1 2+2-
e 3+r 1 2 1 1 1+1-2+r
ag 1+2+ 3 1 1+2+
b a. l-r 3 1 1-2-
e(!) 3+ 2 1 1+2+
9
e!l) r 1 1 l-r
e(2)
9
3+ 1 1 1+2+
e~2) r 2 1 1-2-
d ag 1+2+3+3+ 123 1 1 1 1+1-1-2+rr

a. 1-r3-r 123 1 1 1 1+1+1-2+2+r
In (aac) units a l (101), a 2 ( -1/2, fi/2, 1), a 3 ( -1/2, -fi/2, 1).

Q: D3 (32) - a(I/4, 1/4, 1/4); C3 ,(3) - b(OOO), C,(I) - d(I/2, 0, 0).
In (2TC/a, 2TC/a, 2TC/C) units b l (2/3, 0,1/3),
b 2 ( -1/3, l/fi, 1/3), b 3 ( -1/3, -1/fi, 1/3)
K: D3d - r(OOO), Z(I/2, 1/2, 1/2)
C2h - L(O, 1/2,0), F(O, 1/2, 1/2).
4.5.4 Space Groups and Crystal Structures with Tetragonal Lattices

Simple induced reps of space groups with two types of tetragonal lattices
(D!h' Did and D!Z, D!~, D~d) are given in Tables 4.18-22.
The following structures are described by the space group D!h:
a) the host material YBa Z Cu 3 0 6 for the high-temperature superconductor
YBa Z Cu 3 0 6H - D!h[aD 4h (Cul),gC 4v (Cu2,02), dD 4h (Y), hC4v (Ba),
iC zv (OI)];
b) the crystalline high-temperature superconductors TlBazCan - 1 Cun 0 2n + 3 ;
the atomic distribution in these systems depends on the number n of Cu-O
layers:
n = 2 - D!h[aD 4h (Ca), bD 4h (03), dD 4h (TI), gC 4v (Ba), hC 4v (Cu, 02),
iCz)Ol)] ;
n = 3 - D!h[bD4h(04),cD4h(Cul),dD4h(TI),fDzh(01),gC4v(Ca, Ba),
hC 4v (Cu2, 03), iC zv (02)] .
The symmetry of high-temperature superconductors

Bi(TlhSr(BahCan _ 1 Cu n O Zn + 4 is described by the space group D!Z; in this case
also the atomic distribution over Wyckoff positions depends on the n-number
Table 4.18. Simple induced representations of the Dl. - P4/mmm space group
q p r M Z A X R
a b a b a b
alg,u 1 1 t 3+ 1 3+ t 1 2+
a a lg ,,.. 3 3 3 1+ 3 t+ 2 2 t+
big . 2 2 2 4+ 2 4+ tt I 2+
b b29 4 4 4 2+ 4 2+ 2 2 )+
eg,u 5 5 5 5+ 5 5+ 34 34 3+4+
c d c d c d
alg,u t 4 I 3+ 4 2+ 4+ 4+ 3
c alg,u 3 2 3 )+ 2 4+ 3+ 3+ 4
big . 2 3 2 4+ 3 )+ 4+ 4+ 3
d b29 4 I 4 2+ 1 3+ 3+ 3+ 4
eg,u 5 5 5 5+ 5 5+ )+2+ )+2+ 12
e 1 e 1 e 1
a lg ,,", 12 5+ 3+4+ 12 5 5+ 14+ 32'1' 14+
e big . 34 5+ 1+2+ 34 5 5+ 23+ 1+4 23'1'
b29 5 1+2+ 5+ 5 34 )+2+ t+3 24+ 1+3
1 b3g 5 3+4+ 5+ 5 J2 3+4+ 2+4 13+ 2+4
"I
In (aac) units: (100), "2(010), a 3 (001).
Q: D4 .(4/mmm) - a(OOO), b(O,O, 1/2), c(I/2, 1/2,0), d(I/2, 1/2, 1/2); D2h (mmm.) - e(O, 1/2, 1/2),
1(0, 1/2,0).
In (2n/a, 2n/a, 2n/c) units: b l (100), b 2(01O), b 3 (001).
K: D4h - r(OOO), M(I/2, 1/2,0), Z(O, 0,1/2), A(I/2, 1/2, 1/2);
D2h - X(O, 1/2,0), R(O, 1/2, 1/2~
Table 4.19. Simple induced representations of the Did - P4m2 space group
q p r M Z A X R
a,d b,c a,b c, d a b c d a,d b,c a,d b,c

a al I 1 4 1 2 1 4 3 2 1 3 1 3
b a2 3 3 2 3 4 3 2 1 4 2 4 2 4
C b2 2 2 3 2 1 2 3 4 1 I 3 I 3
d bl 4 4 1 4 3 4 1 2 3 2 4 2 4
e 5 5 5 5 5 5 5 5 5 3 4 I 2 3 4 1 2
9 al I 2 5 I 2 5 I 3 I 3
a2 3 4 5 3 4 5 2 4 2 4
b2 5 1 2 5 I 2 I 4 I 4
bl 5 3 4 5 3 4 2 3 2 3
For the direct and reciprocal lattice basis translations see Table 4.18.
Q: Du(4m2) - a(OOO), b(I/2, 1/2,0), c(I/2, 1/2, 1/2), d(O,O, 1/2); C2v (2mm.) - g(O, 1/2, z);
K: D2d - r(OOO), M(l/2, 1/2,0), Z(O,O, 1/2), A(I/2, 1/2, 1/2);
D2h- X(O, 1/2,0), R(O, 1/2, 1/2).
Table 4.20. Simple induced representations of the D1Z - 14/mmm space group
q p r M X P N
a b a b
a l 1+ 1+ 1+ 1 3 1+ T
a lu I- I- 1- 2 4 1- 2+
a a 2g 3+ 3+ 2+ 4 2 2+ 1-
a 2u r r T 3 1 2- 1+
b bl 2+ 2+ 2+ 2 4 1+ T
blu 2- T 2- 1 3 1- 2+
b2 4+ 4+ 1+ 3 1 2+ 1-
b2u 4- 4- 1- 4 2 T 1+
e. 5+ 5+ 3+4+ 5 5 1+2+ 1-2-
eu 5- 5- r4- 5 5 I-T 1+2+
a1g,u
12 12 3+4+ 5 t2+
e bl.,u 34 34 3+4+ 5 1+2
b2.,u 5 5 t+2+ 1 2 1P
bJ.,u 5 5 1+2+ 3 4 22+
ai' b2 14+ 23'1' 44'1' 5 12+

d a 2, b l 2+3 1+4 3'1'3 5 1+2
e 5+5- 5+5- 1+1-2+2- 1 234 1+1-2+T
a. 1+4+ 5+ Tr5- I+T3+r 135 1+1-2+T

I au 1-4- 5- 2+3+5+ 1-2+3+r 2 4 5 1+1-2+T
b. 2+3+5+ 1-4-5- 1-2+4+4- 2 4 5 1+1-2+T
bu Tr5- 1+4+5+ I+T4+4- 1 3 5 1+1-2+2-
In (aae) units: a,(-!.!.!), a2 (!. -!.!), aJ(!.!, -i),

Q: D4h (4/mmm) - a(OOO), b(I/2, 1/2,0);
D2h (mmm.) - e(1/2, 0,1/2); D2A4m2) - d(3/4, 1/4, 1/2);
C2h (. .2/m) - 1(1/2,1/2,1/2),
In (2TC/a, 2TC/a, 2TC/e) units: hi (011), h2 (101), hJ (110).
K: D4h - r(OOO), M(I/2, 1/2, -1/2); D2h - X(O,O, 1/2);
D2d - P(I/4, 1/4, 1/4); C2h - N(O, 1/2,0).
Table 4.21. Simple induced representations of the Dl: - 14 1 1amd space group
q f3 r M X P N
a b
a a, 1+4- 1 1 2 1 l+r
a2 3+r 2 2 2 1 1-2+
b b2 r2+ 1 2 1 2 1+2-
bl 1-4+ 2 1 1 2 1-2+
e 5+5- 3 4 1 2 1 2 1 2 1+1-2+r
c d
c a. 1+2+5+ 1 4 1 2 1 2 1+1+2+2- 1+I-rr
a. 1-2- 5- 24 1 2 I 2 1-1-2+2- 1+1-2+2+
d b. 3+ 4+ 5+ 2 3 I 2 I 2 1+1-2+2+ 1-1-2+2-
b. r4-5- I 3 I 2 I 2 1+1-2-2- 1+1+2+r
The basis translations vectors of direct and reciprocal lattices and coordinates of K -set
points are in Table 4.20.
Q: Du(4m2) - a(OOO), b(1/2, 1/2,0);
C2h (.2/m.) - c(3/8, 1/8, 1/4), d( -1/8, - 318, 1/4).
Table 4.22. Simple induced representations of the Did - 14m2 space group
q f3 r M N P X
a, b c, d a b c d a,b c, d
a al 1 I 2 I 1 2 4 3 I 3
b a2 3 3 4 2 I 2 4 3 2 4
C b2 2 2 I I 2 1 3 4 2 4
d bl 4 4 3 2 2 I 3 4 1 3
e 5 5 5 1 2 3 4 3 4 1 2 1 2 3 4 1 2
The basis translation vectors of direct and reciprocal lattices are in Table 4.20.
Q: D2d (4m2) - 0(000), b(1I2, 1/2, 0), c(3/4, 114, 112), d(1I4, 3/4, 1/2);
K: D Zd - T(OOO), M(1/2, 1/2, -112); CZy-X(O, 0, 112); S4 - P(1I4, 114, 114);
Cs - N(O, 112, 0).
of CuO layers:
n = 1 - D!Z[aD 4h (Cu), eC4v (Sr, Bi, 01, 02, 03)]
n = 2 - D!ZEbD4h(Ca),eC4v(Cu,Bi,Sr,02,03),iC2v(01)]
4.5.5 Space Groups and Crystal Structures with Orthorhombic Lattices

In Tables 4.23-27 simple induced reps of orthorhombic space groups with a
simple orthorhombic lattice (D~h' D~h' D~n base-centered (D~n and body-
centered (D~n orthorhombic lattices are given. The description of these space
groups is the same as in the International Tables.
Table 4.23. Simple induced representations of the D~h - P2/m 2/m 2/m space group
rxyz
q pa STUR q pa r X Y Z S T U R
a J I h 1 J 3+ 4+ 2+ 2 3 4 1+
2 2 2 2 4+ 3+ 1+ 1 4 3 2+
3 3 3 3 1+ 2+ 4+ 4 1 2 3+
4 4 4 4 2+ J+ 3+ 3 2 1 4+
q pa rYZT XSUR q pa ry xs ZT UR
b 1 J 3+ d 1 1 3=1' 2+ 4
2 2 4=1' 2 2 4=1' 1=1' 3
3 3 1+ 3 3 1+ 4+ 2
4 4 2=1' 4 4 2=1' 3=1' 1
q pa rxys ZTUR q pa rz XU YT SR
c 1 1 2+ f 1 J 3+ 4=1' 2
2 2 1+ 2 2 4+ 3=1' t
3 3 4+ 3 3 1=1' 2+ 4
4 4 3+ 4 4 2+ 1=1' 3
q pa rxzu YSTR q pa rx YS ZU TR
e 1 J 4+ 9 1 J 4+ 2=1' 3
2 2 3+ 2 2 3+ J+ 4
3 3 2+ 3 3 2+ 4+ 1
4 4 J+ 4 4 1+ 3+ 2
In (abc) units: u l (100), u 2 (010), u 3 (001).

Q: D2h (mmm) - a(OOO), b(I/2, 0, 0), c(O,O, 1/2), d(I/2, 0,1/2), e(O, 1/2,0), f(I/2, 1/2,0), g(O, 1/2, 1/2),
h(I/2, 1/2, 1/2).
In (2n/a, 2n/b, 2n/c) units: b l (100), b 2 (010), b 3 (OOI).
K: D2h - T(OOO), X(I/2, 0, 0), Y(O, 1/2,0), Z(O,O, 1/2), T(O, 1/2, 1/2), U(I/2,0, 1/2), S(I/2, 1/2,0),
R(1/2, 1/2, 1/2).
a 1 - ag , au, 2 -btg' blu 3 - b2g , b2u , 4 - b3g , b3u '
The symmetry of the high-temperature superconductor YBa 2 CU3 0 7 is de-

scribed by the space group Dih:
D~h[hD2h(Y)' tC 2v (Ba), aD 2h (Cul), qC 2v (Cu2), eD 2h (01), sC 2v (02),
rC 2v (03), qC 2v (04)] .
The symmetry of the orthorhombic modification of La 2 Cu0 4 is described by

the space group D~f:
Dif [aC 2h (Cu),fCs(La, 02), eC 2 (01)]
Examples of structures with the symmetry of space groups D~h and D~f are
given by s("miconductor superlattices (Si)m(Ge)n considered in Chap. 8. An ex-
Table 4.24. Simple induced representations of the Dih - Pmma space group
q p r X Y Z T U S R
a b a b a b a b
a a. 1+4+ 1 1+4+ 1~4~ 1+4+ 1+4+ 1~4~
1 1 2 1 2
au 1~4~
2 1~4~ 1+4+ 1~4~ 1~4~ 1+4+ 2 2 1 2 1
b b. 2+3+ 2 2+3+ rr 2+3+ 2+3+ rr 2 2 1 2 1
bu rr 1 rr 2+3+ rr rr 2+3+ 1 1 2 1 2
c d c d c d c d
c a. 1+4+ 1 1+4+ 1~4~

rr rr 2+3+ 1 1 2 1 2
au 1~4~
2 1~4~ 1+4+ 2+3+ 2+3+ 2~r 2 2 1 2 1
d b. 2+3+ 2 2+3+ rr 1~4~ 1~4~ 1+4+ 2 2 1 2 1
bu 2~r 1 rr 2+3+ 1+4+ 1+4+ 1~4~
1 1 2 1 2
e 1 e 1 e 1 e 1
e al l+r 1 l+r 3+4~ 1+2~ 1+2~ 3+4~ 1 1 2 1 2

a, 1~2+ 2 1~2+ r4+ 1~2+ 1~2+ r4+ 2 2 1 2 1
1 bl 3+4~ 2 3+4~ l+r 3+4~ 3+4~ 1+r 2 2 1 2 1
b, r4+ 1 r4+ 1~2+ r4+ r4+ 1~2+ 1 1 2 1 2
For the direct and reciprocal simple orthorombic lattice translation vectors and the coordinates
of points included in the set K see Table 4.23.
,v -
Q: e,h (.2/m.) - a(OOO), b(O, 1/2,0), c(O, 0, 1/2), d(O, 1/2, 1/2); e e(I/4, 0, z), 1(1/4, 1/2, z).

Dl: - P2dn 21/m 2da space group
q pa r u XZ YSTR
a J 1234 1234 12 12
b 1 1234 1+2+3+4+ 12 12
c a' l+rr4+ l+r3~4+ 11 12
a" 1~2+3+4~ 1~2+3+4~ 22 12
a 1 means two irreps ag and au of point group e,.

For the lattice translation vectors and coordinates of points
included in the set K see Table 4.23.
Q: e,(!) - a(OOO), b(O, 0, 1/2);
e,(.m.) - c(x, 1/4, z).
Table 4.26. Simple induced representations of the Dl: - C2/m 2/c 2,/a the
space group
q fJ r Y ZT R S
a b
a ag 1+3+ 1+3+ I 1+2+ I-r I
a. I-r I-r 2 I-r 1+2+ I
b bg 2+4+ 2+4+ 2 1+2+ I-r I
b. r4- r4- I I-r 1+2+ I
e a 1+1-4+4- 1+1-4+4- 12 1+1-2+r 11

b 2+r3+3- 2+r3+r 12 1+1-2+2- 11
c ag,u 1234 1+2+3+4+ 12 12I+2+ 11
In (abc) units: a l (1/2, -1/2,0), a 2 (1/2, 1/2,0), a 3 (OOl).

Q: C2h (2/m .. ) - a(OOO), b(I/2, 1/2,0); Cj(l) - c(O, 1/2,0);
C z(.2.) - e(I/4 - y, 1/4 + y,I/4).
In (2n/a,2n/b,2n/c) units: hdl, -1,0), h z(110), h3(OOI).
K: DZh - T(OOO), Y(1/2, 1/2,0), Z(O, 0, 1/2), T(1/2, 1/2, 1/2); CZh - S(O, 1/2,0),
R(O, 1/2,1/2).
Table 4.27. Simple induced representations of the Di: - 12,/m 2,/m 21/a space
group
q fJ r X R S T W
a b
a ag 1+3+ 1+3+ 1+2+ 1-2- I+r I 1
a. l-r l-r 1-2- 1+2+ 1-2+ 1 I
b bg 2+4+ 2+4+ 1+2+ I-r 1-2+ 1 I
b. 2-4- r4- 1-2- 1+2+ I+r I 1
c d
c a. 1+4+ rr 1+2- I-r 1+2+ 1 1

a. 1-4- 2+3+ 1-2+ 1+2+ 1-2- 1 1
d bg 3+2+ 4-1- 1-2+ 1-2- 1+2+ I I
b. r2- 4+1+ 1+2- 1+2+ I-r 1 I
e al I+r 2-1+ l+r l+r 1 1

a2 1-2+ 2+1- 1-2+ 1-2+ 1 I
b2 3+4- 4-3+ 1-2+ 1+2- 1 1
b, 3-4+ 4+r 1+2- 1-2+ 1 I
In (abc) units:
a l (1/2,1/2,1/2), a 2 ( -1/2, -1/2, 1/2), a3(1/2, -1/2, -1/2).
Q: C zh (2/m .. ) - a(OOO), b(1/2, 1/2,0);
Czh (.2/m.) - c(I/2, 0, 0), d(O, 1/2,0);
Czv (mm2) - e(z, z - 1/4, -1/4);
hI: [2n/(ac)](cOa), h z : [2n/(bc)] (0, -c,b), h3: [2n/(ab)](b, -a,O);
K: DZh - r(OOO), X( -1/2,1/2,1/2);
CZh - S(1/2, 0, 0), R(O, 1/2,0), T(O,O, 1/2);
Dz - W(l/4, 1/4, 1/4).
ample of a structure with the symmetry of the Di~ space group is given by the
structure of manganese phosphide MnP with four molecules in the unit cell and
all atoms in the Wyckoff position c:
DiHcCs(Mn, P)] .
4.5.6 Space Group Setting and Simple Induced Representations

for Monoclinic Space Groups
The coset representatives gi = (R;lvJ in the decomposition of the little group G"
with respect to its translation subgroup T are defined by the setting adopted for
the space group G, i.e., by the orientation of the axes with respect to the primi-
tive translation vectors. The space groups with cubic, hexagonal, and tetragonal
lattices are given in the International Tables [4.14] in the setting also used in this
book: the main symmetry axis is oriented along the c translation vector of the
crystallographic unit cell; the two other coordinate axes are oriented along the
a- and b-axes (for hexagonal and trigonal lattices the angle between these axes
is 120).
Different orientations of the coordinate system with respect to the primitive
translation vectors are used in the International Tables for monoclinic space
groups: the monoclinic space groups are given in [4.14] in six versions called
different settings, i.e., different assignments of the a, b, c labels and symmetry
directions to the edges of a given unit cell.
If it is necessary to obtain a table of simple induced reps for other possible
settings of a given space group, one has to consider the influence of the adopted
space group description on the table. Let us move the crystal space by the
operation go = (Rolv o) with respect to the coordinate system, i.e., transform any
point y of the direct lattice space by go to the point y' = goY. In particular, any
Wyckoff position q is transformed to the point q' = goq. Designating the space
group G in the new description by C one obtains
(4.5.1a)
(4.5.1b)
(4.5.1 c)
where G" and G, are little and site symmetry groups, respectively. Equation
(4.5.1b) means that an element g" = (R"lv,,) E G" corresponds to the element
gog"g(/ E C", where k' = gok = Rok,
(4.5.2)
The isomorphism relation C'" +-> G" (4.5.1 b) means that a one-to-one correspon-
dence exists between the irreps of space groups CIe' and GIe' This correspondence
is defined by the character relation
k' = Rok ., (4.5.3)
An analogous correspondence holds for the irreps of the point groups G"
and G,:
X(P)(gogg(/) = X(P)(g) ,
(4.5.4)
g=(Rlv)EG"
Let us use in the two different descriptions G and Gof the same space group
the same letter designations for both the direct lattice space points q and q' =
goq and reciprocal lattice points k and k' = gok, respectively. As an example,
we mention the designations used in the International Tables [4.14]: the
corresponding Wyckoff symbols are retained for the points q and q' = goq in
different descriptions of a given monoclinic space group.
The changes in the Wyckoff site description of a crystal structure caused by
the choice of origin and relabeling of equivalent axes are considered in Sect
3.4.2. The results obtained have to be taken into account when one relates the
crystal structure description to a corresponding space group description.
If the same labels are used for the irreps of the isomorphic groups Gk and
G"" the tables of simple induced reps remain the same for both descriptions G
and G of the same space group. At the same time the coordinates of the q-,
q' -vectors and k-, k' -vectors differ.
In practice, the irreps of the space groups G and G(G k and Gk') are gener-
ated by different authors independently without taking into account the
isomorphism (4.5.1b). Let lk,G)(g) and X(x,Y)(g) be the characters of the small
irreps of the groups Gk and Gx(x E *k'). The operation gogg(/ in (4.5.1a) may
not coincide with the coset representative g = (Rlv) = (Elii ll )goggo1 in a new
description.
Using (4.5.2-3) one obtains
(4.5.5)
R- = RoRRo-1
X(k',G)(g) in (4.5.5) is the character of the small irrep of the space group in a new
description G which corresponds to the small irrep (k,O') of the same space
group in the initial description G. If x = k' = gok, one obtains the correspon-
dence between the irreps X(k,G)(g) and X(X,Y)(g) of the groups Gk and Gx by com-
paring the characters X(k',G)(g) and X(X,Y)(g) of the group Gk,.
If x f= gok one has to change first the wave vector x by k' = gox in the star
*k' of the irrep of the space group G(G x --+ Gk')' This procedure is performed in
the same manner using (4.5.1) where the operation go is replaced by go (k' = gox,
go E G). The correspondence between the irreps of the point groups G, and G"
is defined completely by (4.5.1c) and (4.5.4).
Table 4.28. Simple induced
representations of the Cih - Pl12,/a
space group
q po rDEY ABCZ
a J 12 1
rD EY
b J J2 J+2+ 1
ry DE
e J 12 J+2+ 1
rE DY
d J 12 J+2+ 1
The direct lattice vectors:

adO, -b,O), a 2(asin 'I, -acosy,O),
a 3 (0,0, e);
Q: Ci(I)a - a(OOO), b(O, 1/2,0), e(I/2, 0, 0),
d(I/2,1/2,0).
The reciprocal lattice vectors:
b l 21!/b(-coty, -1,0),
b2 21!/a(cosec 'I, 0, 0), b 3 21!/e(0,0, 1);
K: C2h - T(OOO), A(1/2, -1/2,0),
B(1/2, 0, 0), qo, 1/2, 1/2), D(1/2,0, 1/2),
E(1/2, -1/2,1/2), Y(O, 1/2,0),
Z(0,0,1/2),
a _ Ci group irreps 1+ - ag , 1- - au
Table 4.29. Simple induced representations of the q. - Al12/a space group

q po r Y AM V L
a b
+ -
ab 1 12 1 11 1+J+ 1+ I-
e d
+ -
cd 1 t2 )+2+ 1 1+ 1- 1 +)+ JJ
e a 1+1- 1 1+1- 1+1-

b 2+r 1 1+1- 1+1-
The direct lattice vectors:

al(O, -b,O), a2(a/2sin 'I, -a/2cosy, -c/2),
a 3 (a/2 sin 'I, -a/2cosy,c/2);
Q: ci(I)a - a(OOO), b(O, 1/2, 1/2), c(O, 1/2,0), d(I/2, 1/2,0);
C 2 (2) - e(I/4, z, z).
The reciprocal lattice vectors:
b l 21!/b(-coty, -1,0), b 2 (21!/ac)(ccosecy,0, -a), b3 (21!/ac)(c cosecy,O, a);
K: C 2 - T(OOO), Y(O, 1/2, 1/2), A(I/2,0,0), M(I/2, 1/2, 1/2);
Ci - V(O, 1/2,0), L(l/2, 1/2,0).
Q -1 - a g , all
The procedure described is valid for both the single- and double-valued
induced reps and allows one to generate the table of simple induced reps of a
given space group for any new description G if this table is known for some
space group description G. It is obvious that the same table may be generated
also in the usual way by using the description Gfrom the beginning.
Simple induced reps for the space groups qh and qh with monoclinic
Bravais lattices are given in Tables 4.28 and 29. In these tables the setting with
"unique axis C', cell choice 1" was used [4.14]. The space group C~h corresponds
to a simple monoclinic lattice, the space group C~h to a base-centered
monoclinic lattice. In the setting chosen the second order symmetry axis (unique
axis) is directed along the basis translation vector C of the crystallographic unit
cell. The "cell choice" depends on the choice of the oblique axes with respect to
the glide vector or cell centering vector [4.14]. Examples of structures with
monoclinic space groups are baddeleyite Zr0 2 structure with four formula units
in the primitive unit cell and with all atoms in a general Wyckoff position
e-C~h[eCl(Zr,Ol,02)]; and copper oxide CuO structure (two formula units
in primitive unit cell)-C~h[cCi(Cu),eC2(O)].
5. Application of Induced Representations
in the Electron Theory of Molecules and Crystals
We shall demonstrate that the use of the site-symmetry approach and simple induced representation
tables allows one to quickly analyze the symmetry of crystalline orbitals in complex crystals, despite
the many atoms in a unit cell, and also to draw some qualitative conclusions about the character of
chemical bonding, provided the symmetry properties of the electron states in the upper valence
bands are known.
5.1 Adiabatic and One-Electron Approximations
The complex quantum mechanical systems that are molecules and crystals,
consisting of a great number of atomic nuclei and electrons, can in many cases
be modeled by the non-relativistic Hamiltonian having the form
2N, No
fl = -(h2/2m) L Ar, -
i=l
(h 2/2) L (l/MJA R . + V(r,R)
j=l J
, (5.1.1)
where ri are the coordinates of electrons (i = 1,2, ... , 2N e), Rj are the coordi-
nates of nuclei (j = 1,2, ... , N a ) and V(r, R) is the energy of the Coulomb inter-
action of electrons and nuclei:
V(r,R) = L (ZjZr e )!1Rj -

j<j'
2 Rrl + L e /l ri -
i<i'
2 ri,1 - L (Z e )/lri -
ij
j
2 Rjl
(5.1.2)
The Hamiltonian (5.1.1) is approximate as it does not take into account

the spin-orbit interaction and other relativistic effects. The calculation of
eigenfunctions and eigenvalues of the operator (5.1.1), i.e., the solution of the
time-independent Schr6dinger equation
flf!> = Ef!> (5.1.3)
is possible only after applying some approximations [5.1]. The first of them is
the adiabatic approximation. It permits the motion of electrons and nuclei to
be considered separately and is based on the great difference of electron and
nuclear masses (m M j ).
In the adiabatic approximation, first the problem of electronic motion is
solved for fixed positions of nuclei
[ - (h 2 /2m) ~ A r, + V(r, R) ] IjJ = W(R)IjJ(r, R) (5.1.4)

126 5. Application of Induced Representations
The wave functions t/I(r, R) and the eigenstates W(R) in (5.1.4) depend on the
nuclear coordinates R being parameters. Then the found eigenvalues W(R) are
used as the operators of potential energy in the equation determining the
nuclear motion:
[( -h2/2m) ~ {l/M )L1

j Rj + W(R)] X(R) = t:X(R) . (5.1.5)
This way of solving (5.1.3) is equivalent to the representation of the wave func-
tion W in the form of the product
w(r, R) = t/I(r, R)x(R) . (5.1.6)
Further corrections of this reasonable approximation may be obtained from

adiabatic perturbation theory by using as the small parameter the value
(m/M)1/4 where M is the average mass of the nuclei.
Equation (5.1.4) is often considered as an independent problem without any
relation to the more general problem (5.1.3). This is motivated by the following
reasoning. If the temperature is not very high, the nuclei vibrate about some
equilibrium positions R(O). Thus, in calculating the electronic structure, only the
configuraton with the nuclei fixed at their equilibrium positions R(O) is consid-
ered. The latter are typically known from experimental data (e.g., from X-ray
crystallographic data). This way of electronic structure calculation without
using any other experimental data (except the equilibrium positions of nuclei)
is often considered as made from first principles.
We write the equation for the electronic function of the system in the form
(5.1.7)
where
HO(r i ) = -(h 2 /2m)L1 ri - L (Z e 2 )/lri -
j R}O)I
j
+ (2Netl L (ZjZj'e
j<j'
2 )/IR}O) - Rj?) I (5.1.8)
We assume here that there are a finite number of electrons in the system. This is
certainly true for molecules, but for crystals it implies that we are using the
model of a finite but boundary-less crystal (cyclic model), i.e., we consider the
bulk of a crystal with cyclic boundary conditions imposed on opposite sides.
The symmetry group of such a system G(A) was considered in Sect. 3.3.2. Later
on we call it the symmetry group of a crystal. The Hamiltonian He, being an
operator acting on the functions depending on the electron coordinates r i , is
invariant under symmetry operations transforming the nuclear equilibrium con-
figuration into itself.
Equation (5.1.7) is still very complex. Its solution is not yet possible without
further simplifying approximations. The variables (electron coordinates) cannot
be separated in (5.1.7) because of the terms describing the mutual Coulomb
5.1 Adiabatic and One-Electron Approximations 127
repulsion between electrons. That is why the exact many-electron wave function
t/Imay not be represented as a product (or the finite sum of products) of one-
electron functions. However, the approximate wave function IjJ may be taken
as a sum of the products of one-electron functions, which have to be chosen so
that the approximate function V; is as close as possible to the exact solution 1/1.
The Hamiltonian He does not contain the spin operators. Therefore the
one-electron functions may be expressed in the form of the product qJ(rJll(O"J
of functions qJ(rJ depending on the spatial coordinates of electrons and
functions ll(O"J depending on spin variables only. The function t/I has to be
antisymmetric under the exchange of any pair of electrons. This requirement is
satisfied by the anti symmetric product of one-electron functions
(5.1.9)
The function t/I has to transform according to one of the irreps of the sym-
metry group G. We restrict ourselves to calculation of the ground state of the
system. The latter is assumed to be invariant under the elements of the symme-
try group G and to correspond to a total spin equal to zero. In this case the wave
function may be written in the form of a single determinant (one-determinant
approximation).
In the Hartree-Fock method (also known as the one-electron approxima-
tion or self-consistent field method) the system of equations for one-electron
functions is obtained from the variational principle minimizing the functional
E = J t/I*Het/ldr , (5.1,10)
provided
JqJf(r)qJi,(r) dr = 15;;- (5.1.11)
The supplementary conditions (5.1.11) are not the primary restriction of gener-
ality. Indeed, the orthogonalization procedure of one-electron functions may be
fulfilled directly in the determinant (5.1.9) without any change in its value. The
same condition (5.1.11) assures the normalization of the function t/I to 1. The
one-electron functions satisfy the following system of Hartree-Fock equations:
HHF({Ji(r) = L ei'i({Ji,(r) (5.1.12)
i'
or
HHP({J = ({Je , (5.1.13)
where the Hartree-Fock operator
HHF=Ho+J-K (5.1.14)
is defined below, ({J is a row of functions ({Ji' and e is the matrix of coefficients en.
In the Hartree-Fock operator HHF the term Ho is the one-electron operator
(5.1.8). The action on the function ((Ji(r) of the Coulomb operator J and ex-
change operator K is determined in the following way. Denote by p(r,r') the
mixed electron density with fixed spin (electron density matrix)

N,
p(r,r') = I (fJi(r)(fJ~(r') = (fJ(r)(fJ+(r') , (5.1.15)
i=l
where (fJ + is the column of functions (fJ* (r'). Then
~
J (fJi(r) = 2e
2 f Ir _ r'l
p(r',r') ,
dr (fJi(r) ,
(5.1.16)
K~ (fJi ()
r =e
2 f Ir _ r'l
p(r, r')
(fJi
(') d '
r r.
The operator J is the potential energy operator of an electron in the Coulomb

field created by all the electrons of the system, with the electron in question
included. This is a usual multiplication operator. It acts on the functions de-
pending on the space coordinates of an electron. The Coulomb operator is
determined if the electron density p(r', r') is known. The operator If is an inte-
gral nonlocal operator with the nucleus p (r, r')/ 1r - r' I. To calculate the func-
tion K(jJi it is necessary to know the function values in the entire domain of its
determination. The operator f'l (5.1.14) is self-adjoint, as p(r,r') = p*(r',r).
Multiplying both sides of (5.1.12) by (fJ!(r), integrating over dr and using the
orthonormality of the functions (fJi(r), we obtain
(5.1.17)
The matrix e in (5.1.13) is hermitian. It may be diagonalized with the help of a

unitary transformaton U:
1ifJU) = (fJeU = fJU)(U- 1 eU) , (5.1.18)
where U- 1 eU is a diagonal matrix. The unitary transformation U (UU+ = 1)

does not change the electron density matrix
(5.1.19)
Then this transformation keeps the Coulomb J and exchange If operators

invariant (and the total Ii). Therefore, without any restriction on the generality
the matrix e in the right-hand side of (5.1.13) may be considered as diagonal
(5.1.20)
The system of Hartree-Fock equations (5.1.20) is nonlinear. To solve it an
iterative method is usually used. In the course of the pth iteration the electron
density matrix p(Pl(r, r') and hence the operators J and If are considered to be
fixed. The system (5.1.20) then transforms into one linear equation with a fixed
self-adjoint operator
5.1 Adiabatic and One-Electron Approximations 129
The eigenstates of this operator corresponding to the lower eigenvalues are

populated with electrons. The occupied states are used to construct p<P+1)(r, r')
according to (5.1.19) and then j(p+1) and K(p+l) according to (5.1.16). Then the
subsequent iteration is performed. The procedure of solution is stopped when
the functions cpjP) approach cpjP-l)(r) (within the desired accuracy). In practice,
other criteria are also used to estimate the accuracy of the obtained solution.
Thus, by an iterative method a self-consistent solution of the nonlinear
equations (5.1.20) may be obtained. The rate of convergence of the iterative
procedure depends on the nature of the physical system as well as on the choice
of the initial approximation.
The calculation of the eigenfunctions of the operator BHF during the p-th
iteration is itself a difficult problem which may be solved only approximately.
To simplify it the nonlocal exchange potential K is often replaced by a local
potential. The most widely used form of the local exchange potential is
(especially for crystals)
(5.1.22)
proposed by Slater. The constant a in crystal electronic structure calculations

is an adjustable parameter. If no iterative procedure is performed the electron
structure obtained is said to be non-self-consistent. This kind of calculation is
justified only when the one-electron Hamiltonian Bf/P correctly reflects the
main features of the "true" (self-consistent) energy operator. It is very difficult
to guess such a potential without involving some empirical data. The sum of
atomic (or ionic) potentials is the most simple and natural form of the molecu-
lar or crystal potential in non-self-consistent calculations. It is also used as an
initial approximation in self-consistent electronic structure calculations.
5.1.1 Space Symmetry of the One-Electron Approximation Hamiltonian

The many-electron Hamiltonian He in (5.1.7), acting in the space of functions
depending on the coordinates of all the electrons, is invariant under the rep
operators {j of the equilibrium nuclear configuration symmetry group G. The
operators of electron kinetic energy in (5.1.8) and the Coulomb repulsion be-
tween electrons in (5.1.7) remain unchanged under any transformation belonging
to the Euclidean group E3 since, according to the definition, the elements of E3
are the transformations which do not change the distances between any two
points of the space. As to the operators of electron-nuclear interaction in (5.1.8),
the operations {j permute the members of the sum, leaving the sum as a whole
invariant. Indeed, the coordinate ri transforms under g in
r; = gri (5.1.23)
and the denominator Iri - RjO) I in (5.1.8) becomes equal to

130 5. Application ofInduced Representations
Ir; - RjO) I = Igr j - RjO) I = Ig('i- g-l RjO)1

= Iri - g-l RjO) I , (5.1.24)
i.e., to the denominator of other members in the sum in (5.1.8). This reasoning
also proves the invariance of the one-electron operator fi (5.1.8) under the
transformations 9 from the group G.
The set of one-electron functions transforming according to the np-
dimensional irrep D<P) [for a crystal P = (*k, y)] of G is called the shell. Taking
into consideration the spin states x(a) we have 2np one-electron states in the
shell. The functions cplP)(r)x(a) span the space of the rep D<P) x D1/2, where D1/2
is the rep according to which the spin functions transform (Sect. 3.6). The deter-
minant (5.1.9) consisting of the functions of filled shells describes the state
invariant under the operations of the group G (unity irrep of G). In fact any
transformation of G replaces the columns of the determinant by their linear
combinations, which does not change the value of the determinant, i.e., does not
change the many-electron wave function t/J.
Now we check that the group G is a symmetry group of the Hartree-Fock
equations (5.1.20). First we note that the sum
(5.1.25)
is invariant under the group G (Sect. 2.3.1, identity irrep of G). The electron
density matrix p(r, r/) is also invariant under G because for filled shells it is the
sum of terms like (5.1.25)
p(gr, gr/) = p(r, r/) . (5.1.26)
The operators fi (5.1.14) and HIt (5.1.21) are one-electron, i.e., they are
determined in the space of functions depending on the coordinates of one
electron.
The invariance of the operator fio is already proved. For Coulomb J and
exchange K operators and for an arbitrary function cp(r) we have
~ p(r' r')
gJcp(r) = 2e 2 f I l' 'I dr' cp(g-l r)
9 r - r
= 2 2 fP(g-lrl,g-lrl) d( -lr') ( -l r )
e l9l r - 9 1
r 'I 9 cp 9
p(r' r/) ~
= 2e 2 f - - '-dr' cp(g-lr) = Jgcp(r) ; (5.1.27)
Ir - r/l
gKcp(r) = e2 f Ip(g -lr'IIr') cp(r') dr'

9
1
r - r
p(r,r/) ~
e 2 f --cp(g-lr /)dr '
A
= = Kgcp(r) . (5.1.28)
Ir - r/l
The relation (5.1.26) and the equality Ig- 1 r-g- 1r'l = Ir-r'l and
d(g -I r') = dr' are used to prove the invariance of HHF' As (5.1.27 - 28) hold
for an arbitrary function cp(r),
(5.1.29)
and therefore
[ gHHF = HHFg, gHYI~ = HYI~g . (5.1.30)
Thus the operator HHF(HYI~) in the electron equation (5.1.20) has the sym-
metry group G of the equilibrium nuclear configuration if the electron density
matrix p(r,r')[p(p)(r,r')] is invariant under G. The eigenfunctions of the
operator HHF(HYI~) form the bases of irreps of G. The invariance of p(r,r')
. [p(P)(r,r')] is assured for the system with filled shells.
Thus, taking as the initial approximation that the electron density p(O)(r, r')
is invariant under the group G we shall have, during any iteration step and
in the self-consistent limit, the one-electron functions classifying according to
the irreps of the group G-the symmetry group of the equilibrium nuclear
configuration.
In the absence of external fields the realness of the one-electron Hamil-
tonian is assured at all stages of the self-consistent calculations, at least for a
system with filled shells. The realness of the HamiltonianHYI~ (5.1.21) leads to
the real electron density matrix p(P+l)(r, r') generated by the eigenfunctions of
HYI~. Indeed, let the functions cp\P)(r) and (cp\P)(r* belong to the same one-
electron energy and describe the occupied electron states. If they span the space
of the same irrep D(P) of G (D(P) is real) then the partial sum (5.1.25) formed by
these functions and involved in pep +1)(r, r') is obviously real. If they are the
independent bases of the irreps D(P) and (D(P* (equivalent or inequivalent) then
the sum of two terms of the type (5.1.25) is also real. This is the case of additional
degeneracy due to the Hamiltonian being real. Thus, the electron density matrix
is the sum of real members and is real itself. The real density matrix p(P+1)(r,r')
generates the real Coulomb J(p+l) and exchange K(p+1) operators and therefore
the real one-electron HamiltonianHYI; 1) for the (p + l)-th iteration of the self-
consistent calculations.
5.2 Induced Representations in the Electron Theory of Molecules
5.2.1 Canonical, Localized and Hybridized Molecular Orbitals

As we have seen in Sect. 2.3.3 the symmetry-adapted basis "'k~(r) in the space
of an induced rep d(P)jG may be obtained with the help of a reduction matrix
from the basis of localized functions W;)p)(r). We rewrite (2.3.50) in notations

usual for the description of electronic states
t/llc"J(r) = L ([3ijlrxkJ-l) W;YI)(r)

ij
. (5.2.1)
Because the reduction matrix is unitary the reverse transformation takes the
form
W;YI)(r) = L ([3ijlrxkJ-l)*t/li~(r)
ak/l
. (5.2.2)
If the occupied one-electron states of a molecule span the space of an induced

rep d(P)jG then (5.2.2) can be used to generate the functions W;)P) related to this
set. The functions W;YI) have the symmetry properties of localized functions. In
particular, they transform according to the irrep [3 of site group Gj (for fixed j).
But they may not manifest a clearly expressed space localization. The degree of
space localization of these functions is defined by an additional criterion. To
generate the most localized functions possible (according to the chosen crite-
rion) one makes use of the arbitrariness which exists in the choice of basis in the
space of the induced rep.
In the self-consistent calculations of molecular electronic structure one
obtains molecular orbitals (also called canonical orbitals) qJi~(r). If the irrep rx is
contained more then once in d(P)jG (r~Pl > 1) then it is possible to write arbitrary
linear combinations of canonical orbitals qJi~(r) with different J-l
t/I~~(r) = L e~~~qJ~~,(r)
/l'
. (5.2.3)
The functions t/li~ transform according to the irrep rx with the same matrices
D(a)(g) as the functions qJi~(r). The coefficients e~~~ form a unitry matrix era) if
the bases t/I~~(r) and qJ~~(r) are orthonormal. The matrix era) is orthogonal for
real basis. Substituting (5.2.3) into (5.2.2) we relate the localized functions
W;)p)(r) to canonical orbitals qJ~~(r) by
W;)pl(r) = L (rxijlrxkJ-l)* L q~~qJlc"J,(r)

ak/l /l'
(5.2.4)
containing arbitrary constants q~~. They may be used to get the functions
W;)p)(r) to be as localized as possible. In practice it is sufficient to determine the
functions W;l!)(r) since the others (for j "# 1) will be found according to (2.2.36).
Therefore it is necessary to know only the elements of the first block row of the
reduction matrix (Sect. 2.3.3).
Recall that the canonical orbitals must be chosen so that they transform
with the same matrices D(a) of the irrep rx which were used for the determination
of the reduction matrix. If a set of canonical orbitals does not span the space of
some induced rep of a molecular symmetry group G and is not a direct sum of
the latter, then no linear combinations of canonical orbitals from the set lead to
any localized functions.
This method of localized function generation does not depend on the basis
that was used for the calculation of canonical orbitals. In the electron theory of
molecules these are the functions of atoms composing the molecule, which are
often used as a basis (MO LCAO approximation)
(5.2.5)
Then the localized orbitals (5.2.4) are also some linear combinations of atomic
functions. Some coefficients of these linear combinations are coupled to one
another by relations stipulated by symmetry considerations. The localization of
the ~yl) functions generated in the LCAO basis is shown by a decrease in the
atomic function coefficients with increasing distances between atoms and the
center of the localization of the function.
Let us consider how to establish the symmetry relations between the coeffi-
cients in linear combinations of atomic functions forming a localized orbital. Let
a localized orbital ~)fI)(r) transform according to an irrep dIP) of the site group
G, of a point q. The point q may occupy a position on the symmetry line or on
a symmetry plane. Generate from the atomic basis functions the linear combi-
nations spanning the space of the irrep dIP) of G,. If the irrep dimension np is
greater than 1 we can restrict ourselves to generating only one basis vector (e.g.,
the first one, i = 1). If it is necessary, the others may be obtained from the first
one by applying the operators pff) (Sect. 2.2.2). All the atoms of the molecule are
divided into orbits with respect to the site group G,. If an atom is alone in an
orbit (its site group with respect to G, coincides with G, itself) then it is easy to
pick out of its atomic functions (s, p, d and so on) those that span the space of
the irrep dIP) of G,. To do this, the irrep D~~~ (j = 0,1,2, ... ) of 0(3) must be
restricted to elements of G,. Then it is necessary to define which of these
subduced reps contain the irrep dIP) of G, and also how many times they contain
it. Then the linear combinations are generated with the help of the operators
Pff>. These combinations arc given in Table 3.7 for s-, p-, and d-functions.
If an orbit consists of several atoms then the site symmetry group of each of
them (with respect to G" not to G) is a subgroup of G ,. We choose from the
orbit one of the atoms with site group NeG, and restrict the irrep dIP) of G, on
N,
(5.2.6)
where ,d(a) are the irreps of N. If r!P) =f. the rep of G, induced by the irrep ,d(a)
of N contains r!p) times the irrep dIP) of G,. Thus, first find the linear combina-

tions of atomic orbitals transforming according to the irreps ,d(a) of N [for
r~P) =f. in (5.2.6)J and then, acting on them by the operators pff), construct the
combinations transforming as the first basis vector of irrep dIP). After this con-
struction is done for all the orbits in the molecule, we can number the obtained
functions with the index J.1.: fl(~)(r). All the atoms of a given orbit are at the same
distance from the point q. The functions fi~) are assumed to be numbered in
order of increasing distance from the point q to the atoms where they are
centered. The function
W1(1)(r) = L CJ1(~)(r) (5.2.7)

I'
with arbitrary coefficients CI' is the most general expression for the orbital
transforming as the first basis vector of the irrep dIP) of G,.
Equation (5.2.7) may also be obtained in another way. Consider the
occupied electron canonical orbitals in the molecule which span the space of
several induced reps (q, (3) and have energies relatively close to one another. In
this case all the canonical orbitals should be involved in the generation of the
localized function. If some irrep D(a>, according to which the canonical functions
transform is contained in several induced reps (q, (3), these functions can take
part in the formation of several different localized functions. Let an induced rep
(q, (3) be fixed. In the space of all canonical functions <Pk~ we form the subspace
of the first basis vectors of the irrep d(P) of the site group G,. Only those canoni-
cal functions that span the spaces of irreps of G which determine the index of the
induced rep (q, (3) in k-basis
./,(P) -
'1'1 -
pep) mea) -
11 'l'kl' -
'\'
L...
bk'k'l'k'l'
mea) (5.2.8)
k'
have a nonzero projection in the subspace mentioned above. We number them

by an index p and form the linear combination
w'(P)(r) = '\' a ./,(P) (5.2.9)
11 L... p'l'lp'
P
The coefficients ap should be chosen so that the function is as localized as

possible. The sum (5.2.9) may be represented in the form of (5.2.7) since the
functions 1jJ!fJ(r) are also linear combinations of atomic orbitals spanning the
space of the first basis vectors of the irrep dIP) of the site group G,:
IjJ<tJ = I dl'pfl(~)(r) . (5.2.10)
I'
Substituting (5.2.10) into (5.2.9) and comparing with (5.2.7), the coefficients Cl'in
(5.2.7) seem to be linear combinations of the coefficients a p in (5.2.9). The latter
should be chosen in such a way that the coefficients CI' decrease in absolute
value with the numbers Jl as quickly as possible.
If the groups of energy levels belonging to different sets of canonical orbitals
spanning the spaces of induced reps are separated from one another by compara-
tively large energy intervals then every set can be treated independently of the
others. This case is the simplest to consider. Otherwise special attention must be
paid to the orthogonality of spaces corresponding to different induced reps.
When the point q lies on the line passing through atoms A and B, the group
GIJ (= Cn' Cnv ) is a symmetry group of the bond AB. Let, in a given localized
function (5.2.7) of symmetry {3 (irrep d(P) of Gf)' the coefficients at orbitals of
atoms A and B be large and the rest be negligible. This is the case of the
localized function describing a two-center bond. As we shall see, it consists of
two hybridized orbitals of atoms A and B. Let A be a central atom with the site
symmetry G" = G coinciding with the symmetry of the molecule and let B be
one of the symmetrically equivalent ligands. By definition, the hybridized or-
bital of the central atom is such a linear combination of initial atomic orbitals
that represents the atom A in the localized orbital of the bond AB. Other
hybridized orbitals of the central atom are obtained by applying to the first one
the operators gj (G = LjgjG", gj --+ (j). They represent the central atom in other
two-center localized orbitals, describing its bonds with the other symmetrically
equivalent ligands B(j).
The functions of atoms A and B may have different weights in the localized
orbital of the bond AB. This difference of weights reflects the fact that the point
q is nearer to one or the other atom. In the limiting case when the localized
function consists of atomic functions of only one atom (A or B) it describes a
lone electron pair on one of the atoms.
The set of two-centered localized orbitals under consideration forms a basis
of an induced rep of symmetry group G of the molecule. It consists of some
irreps of G: 1'1' 1'2' .... Under the operation (j (g E G) the central atom functions
transform into each other. Therefore, those of them that take part in the local-
ized orbitals (hybridized function of the central atom) themselves form the basis
of the direct sum of irreps 1'1' 1'2' ... , i.e., the basis of an induced rep.
To construct the hybridized orbitals of the central atom A which are com-
patible with the site symmetry of the bond (irrep d(P) of site symmetry group GII)
it is necessary
1) to determine irreducible components 1'1' 1'2' .. , of the rep induced by the

irrep d(P) of G c G'
2) "
to pick out from ' the set of atomic functions those which transform
according to the irreps 1'1' 1'2' ... of G (the number of atomic functions
should not be less than the dimension of the induced rep);
3) to construct the linear combinations transforming according to irrep /3 of
GII (it is sufficient to construct, for example, the first basis vector of the irrep
/3, if it is multi-dimensional);
4) to multiply the functions obtained by arbitrary coefficients and to add;
5) to obtain the other basis vectors of the irrep /3 with the help of the operators
Pg);
6) to generate the other hybrid orbitals by application of operators gj (gj E G)
to the obtained orbitals.
The localized orbitals may span the space of any irrep of the site group
Gq Thus the corresponding hybridized orbitals seem to be also contained in
localized orbitals of any given symmetry. Most often the hybridized orbitals are
considered to form the space of the identity irrep of a site group Gq However,
symmetry constraints do not allow one to consider this particular case as the on-
ly possible one. A given geometry of a molecule does not preclude the genera-
tion of localized and hybrid orbitals with any symmetry (i.e., transforming ac-
cording to any irrep of site group G q ).
The contribution in the electronic density of localized orbitals w,J) (for

fixed 13 and j) is equal to Li
1W/f> 12 and is invariant under the operations of the
bond site group G,. The contribution in the electronic density of the whole set
of localized orbitals (for fixed 13) is equal to Lij
1 W;}fJ)1 2 and is invariant with
respect to the full symmetry group G of a molecule.

The atomic functions of s-,p-, d- ... type can participate in the construction
of a hybridized orbital. It is obvious that the symmetry relations can hold only
between the coefficients of atomic functions with the same orbital quantum
number 1 (only p-functions, or only d-functions and so on). The relations be-
tween the coefficients which are not due to symmetry may be obtained only as
a result of molecular electronic structure calculations or supplementary
conditions imposed on the orbitals. The case of a multi-centered bond may be
considered in the same way.
5.2.2 Localized Two-Center Bonds and Hybridized Orbitals

in AB" and AB3 Molecules
In a tetrahedral AB4 molecule (Fig. 5.1) with symmetry T.! the atom A occupies
the position in the center of the tetrahedron (site symmetry GA = T.!); the ligands
B(i) (i = 1,2,3,4) are situated at its vertexes.
Let q be the point at the bond line AB(l) with the site symmetry G, = C 3v .
This group is also the site symmetry group of the ligand B(1). Using the s- and
p-functions of the atoms A and B(i) let us construct the functions of the most
general form transforming according to the irrep a l of the group G, = C 3v . This
irrep induces the rep a l + t2 of the molecular group T.! (Table 4.2). There are
three orbits in the molecule AB4 with respect to the bond site group G, = C 3v :
A; B(l); B(2), B(3), B(4). In the space of s- and p-functions of atoms A and B(l) the
linear combinations with the symmetry a l of G, = C 3v are constructed directly
({Jl = S ; ({J2 = Px + Py + pz ;
(5.2.11)
({J4 = p~l) + p~l) + p~l)
/..--
8(2)
L_--I __
: I
I I A
I 1 y :
1 x I I
I /L----l--,e
..L./"
8(3) _ _ _ - - - -
I /
-.V
8(4)
Fig. 5.1. A tetrahedral molecule AB4
The site group of the ligand B(2) with respect to G" = C 3v is N = Cs It consists
of two elements (E,a xy ) and has two irreps: a' and a". The irrep a l of Gf = C 3v
is contained in the rep induced only from the irrep a' of N = Cs (Table 4.2). The
spaces of this irrep are spanned by the following S-, p-functions of the ligand
B(2):
(5.2.12)
Applying the operator p(a d to these functions we get the following linear combi-
nations with symmetry a l of G" = C 3v :
CP6 = (pf) + p~2) + (p~3) + p~3) + (p~4) + p~4) (5.2.13)

rn =
'1'7
p(2)
z
+ p(3)
x
+ p(4)
y'
So the most general form of the function with symmetry a l of G" = C 3v in the
space of S-, p-functions of the atoms in the molecule AB4 is
7
w(a,) = "1-, C.rn.
J'I'J' (5.2.14)
j=1
where the functions CPj are taken from (5.2.11, 13). The coefficients Cj cannot be
determined from symmetry considerations. The natural criterion of localization
on the bond AWi ) for the function (5.2.14) is the small value of the coefficients at
the functions centered on the atoms remote from the bond. In the given case
these are the atomic functions of the ligands B(2), B(3) and B(4).
If the electronic density in the AB4 molecule is indeed localized on the
bonds AB(i) (Cj = 0, j = 5, 6, 7) then the function w(a d has the form
w(a')(r) = cp~I)(r) + cp~(ll(r) , (5.2.15)

where
cp~;>(r) = CIS + C 2 (Px + Py + pJ (5.2.16)
cp~ll(r) = C 3 S(I) + C4(p~l) + p~l) + p~1)) (5.2.17)
are the hybrid orbitals of atoms A ad B(I) in the molecule AB4 . The representa-
tives gi in the decomposition
G = I:J = L gjG" = L gjC 3v (5.2.18)

j j
may be chosen so that they form the group D2 (I:J = D2 x C 3v )' Therefore other
localized and hybrid orbitals may be obtained by applying the operators
D( C 2z ), D( C 2 J, D( C 2y ) (C 2x , C 2y , C 2z ED2)to (5.2.15-17). In particular, in addi-
tion to (5.2.16) we get for the central atom A three more hybrid orbitals
qJ~i)(r} = ClS + C z( - Px - Py + pz} ,
qJ~j)(r} = ClS + Cz(Px - Py - pz) , (5.2.19)
qJ~~)(r} = ClS + C z( - Px + Py - pz)
The coefficients C l and Cz are obtained in the electron structure calculations.

The values of coefficients Cj depend on the interelectron and electron-nuclear
interactions in the molecule. Often the idealized hybrid orbitals of the type
(5.2.15, 19) are considered when they are submitted to supplementary ortho-
normalization conditions. Then C l = C z = 1/2. This is the so-called Sp3 hybrid-
ization. The hybrid orbitals calculated according to the procedure described
only approximate the idealized ones.
As we see from (5.2.17) a hybrid orbital of corresponding type is formed also
for the ligands. Four hybrid orbitals corresponding to the site symmetry of the
bond (and of the atom) may be constructed from four atomic s- and p-functions.
Besides (5.2.17) there is one more hybrid orbital with the same a l symmetry [but
with other coefficients C 3 and C4 in (5.2.17)] and two hybrid orbitals with the
symmetrye of C 3v :
qJ\e) = (2p~1) _ p~l) - p~l))/ J3 ;
(5.2.20)
Whether these orbitals participate in the formation of some localized orbitals

depends on the nature of the atoms constituting the molecule. In the molecule
CCl 4 these orbitals themselves form the localized orbitals describing the lone
electron pairs on the CI atoms.
As another example consider a molecule of type AB3 with the symmetry
G = C 3v ' The AB bonds have the symmetry Cs The atomic arrangement with
respect to the coordinate system is shown in Fig. 5.2. Let us generate from the
functions of atom A the hybrid orbitals of symmetry a' (a' is the unit irrep of the
site group Cs of the bond). This irrep induces in the group C 3v the rep a l + e
(Table 4.2). To construct one of the hybrid orbitals it is sufficient to pick out the
.._----.L--+------:~ S(2)
Fig. S.2. A molecule AB3 and its arrangement with

x
respect to the coordinate system
atomic functons with the symmetry a 1 and e of the group C 3v and to form the
linear combination transforming according to irrep a' of Cs Among the s- and
p-functions, the s- and pz-functions have the symmetry a 1 and the Px, Py-
functions have the symmetry e. Of these, only S-, pz- and px-functions transform
according to irrep a' of Cs . So
(5.2.21)
The coset representatives in the decomposition of C 3v with respect to Cs form a

group C 3 (E, C 3z , C 3;). Therefore other hybrid orbitals are obtained from
(5.2.21) by the rotations D(C 3z ) and D(C 3;):
CfJA2 = C1s + C 2 Pz + C 3 (-Px + J3p y}/2

(5.2.22)
5.2.3 Multicentered Bonds in the 1, 6-C2B4H6 Molecule

The symmetry analysis of chemical bonds in the molecule 1, 6-C 2B4H6 is based
on results of self-consistent calculations of its electronic structure [5.2]. The
arrangement of atoms in the molecule is shown in Fig. 5.3. The core states are
excluded from our discussion; the scheme of one-electron levels and their sym-
metry are given in Fig. 5.4. The 1, 6-C2B4H6 molecule has D4h symmetry. The
site symmetry groups are C4v , C~v' C~v, C;, C;', C;'. We partition the states into
sets according to the symmetry so that each set is the space of some rep of
G = D 4h induced by an irrep of some site group:
(b 2g ) . (5.2.23)
Fig. 5.3. Structure of 1,6-C2B4H6

Fig. 5.4. One-electron levels and their

symmetry for the 1,6-C 2 B4 H 6 molecule
L "'--L-----..L-.L.~1_\--L---l...-\\J...I...-.l.--ITr~
C 4v (a,) C2v (a,) C4v (e)
L",-l ' - -_ _ _....
1 ...... L.J
C4v (a,)
This partition seems to be unique. The energy levels of the sets are close to one
another and even overlap.
The canonical orbital with symmetry bzg is simultaneously a localized one
describing the four-centered bond between B-atoms. The site group of this bond
(D 4h ) coincides with the full symmetry group of the molecule. The localized
orbitals for four other sets may be constructed as follows. The sets (a lg , a zu ) and
(eu , alg' big) correspond to the C-H bonds (G q = C4v ) and B-H bonds (G q = C2v )'
Taking into account that the molecular orbitals of symmetry alg are repeated
three times in the sets, we maximize, with the help of a unitary transformation,
the absolute values of the coefficients of atomic orbitals participating in the C-H
and B-H bonds. Analogous transformations must be done for the molecular
functions of symmetry a zu and eu. Then we distribute the newly generated or-
bitals (linear combinations of canonical ones) into corresponding sets. Finally,
we construct the localized orbitals (Sect. 5.2.1), choosing the phase multipliers
for the orbitals properly to obtain the maximum possible localization. Thus, one
obtains that one of the sets (a l9 , azJ corresponds to the localized orbitals of the
C-H bond. Moreover, the main contribution to the bond C(1)_H(l) is due to 2s,
2pz orbitals of the C(l) atom and the ls orbital of the H(l) atom. The second set
(a l9 , azJ describes the lone electron pairs on C atoms (linear combination of 2s
and 2p atomic orbitals). The set (a l9 , blg, eu) generates the localized orbitals of
the bond B-H. In particular, the localized orbital of the bond B(Z)_H(Z) consists
se
mainly of 2s and 2px orbitals of the Z) atom and the ls orbital of the H(Z) atom.
Lastly, the set (e g , eu ) corresponds to the localized orbital describing the three-
centered CB l bonds between a C atom and a pair of non-neighboring B atoms.
For example, the function localized on the three-centered bond C(l)B(l)B(4)
consists of the 2px orbital of C(l) and the 2s and 2pz orbitals of atoms l ) and se
B(4).
5.2.4 Canonical and Localized Orbitals in the MnO';: Molecular Ion

In this system there are several ways to divide the canonical one-electron
functions into sets, all of which are allowed by symmetry. Table 5.1 lists one-
electron energies of the MnO';: ion valence orbitals calculated by a) the
nonempirical MO LCAO method, b) the SW Xa-method, c) a semiempirical
CNDO method [5.3]. The weights of valence atomic orbitals in molecular or-
bitals are also given in cases a) and c) (in parentheses). The 4s-, 4p-, and 3 d-
functions of the Mn atom span the space of the irreps ai' 12, e + 12 of the
Table 5.1. Electronic structure of MnO"
One-electron energies [eV] Atomic contributions [%]
State SW X. CNDO Nonemp. 3d 4s 4p 2s 2p

symmetry calcul.
It I -9.28 -7.01 -7.62 - - - - 100

(100)
6a l -10.53 -8.95 -8.03 - 8 - 4 88
(5) (2) (93)
6t 2 -10.37 -9.69 -9.06 3 - 7 2 88
(17) (2) (5) (76)
Ie -12.24 -10.15 -11.48 29 - - - 71
(23) (77)
5t 2 -12.43 -11.26 -12.82 53 - 2 6 39
(18) (7) (4) (71)
4t2 -24.30 -32.68 -29.44 7 - 4 87.5 1.5
(2) (17) (79) (2)
5a l -24.65 -36.43 -30.01 - 7.5 - 91.5 -
(21) (78) (1)
molecular symmetry group 7d. The site symmetry group of the 0 atom is C 3v '
The 2s and 2pz functions of the oxygen atom contribute to the canonical or-
bitals of a 1 and t2 symmetry, and oxygen 2px-, 2py-functions contribute to
functions with the symmetries e, t 1 , t 2 The site group C 3v may correspond to
localized functions centered on oxygen atoms as well as on the Mn-O bond axis.
The site group C 2v may be related to a two-centered 0-0 bond or to a three-
centered O-Mn-O bond. The latter may also have Cs symmetry.
The valence canonical orbitals given in Table 5.1 may be distributed over
sets according to the procedure described above. There are three possible vari-
ants of distribution compatible with the symmetry requirements:
2) C 3v (ad - 5a 1 , 4t2 ; (5.2.24)
C 2 Jbd - 1t 1 , 6t 2 ;
The first variant is the most preferable as it corresponds to two-centered

bonds, whereas the second and the third possibilities contain sets with bonds of
more than two centers. The greater the number of centers participating in a
bond, the less localized it seems to be. Table 5.1 shows that the sets C 3v (a 1 )
correspond to orbitals localized near the oxygen atoms, the s-type is the lowest
in energy and the 2pz-type (directed along the O-Mn line) is higher. The local-
ized functions of C 3v (e) symmetry contain a considerable admixture of Mn 3d-

states. So the center of localization is apparently displaced along the bond line
towards the Mn atom.
Each of the three sets (5.2.24) contains states of t2 symmetry and in two sets
there are states of a 1 symmetry. In accordance with Sect. 5.2.1, when generating
localized orbitals it is possible to take the linear combinations of initial canoni-
cal functions of the same symmetry and to vary the coefficients to get the or-
bitals with the best spatial localization. However, in the case of Mn04" the
orbitals 5a 1 and 6a 1 have considerably different energies. Therefore the linear
combinations must be used only for orbitals of t2 symmetry (especially 5t 2 and
6t 2 )
In [5.3J the analysis of the calculated states was made only according to the
weights of the atomic functions and symmetry considerations were not taken
into account. As a result the 6t 2, 6a 1, 1t1 states are treated as being in the set
corresponding to the localized functions of 2p-type centered on oxygen atoms.
As follows from Table 5.1, these states do not span the space of the rep induced
by some irrep of the site group of the oxygen atom. Therefore it is impossible
to generate any function localized on the oxygen atom. Hence simply the
analysis of the atomic orbital contributions in molecular states with close
energies does not permit one to correctly relate the canonical orbitals to the
localized ones.
As we can see, induced reps of point groups, in combination with an
analysis of the atomic contributions in molecular eigenfunctions, are a good
tool to find the regions of localization of electron density on atoms and bonds
in a molecule. Of course the energy criterion must also be taken into consider-
ation: a set is chosen so as to unite states with close energies.
Table 5.1 shows that the symmetry of localized orbitals does not depend in
practice on the method of calculation of electronic structure. In particular, the
method described here is equally applicable to results of SW Xa calculations
where the atomic basis is not used at all. The change in energy ordering of the
6a 1 and 6t 2 levels from that of the nonempirical method does not change the
symmetry found for the localized orbitals.
5.2.5 Localized Orbitals in the Tetrahedral Bi4 Molecule

When relativistic effects are taken into account, double-valued induced reps can
be used to analyze the localization of electron states. As an example we consider
the ground state of the tetrahedral molecule Bi 4. It has been calculated in rela-
tivistic and nonrelativistic variants of the extended Huckel method in [5.4].
Figure 5.5 shows the one-electron energy levels of the upper occupied and
lowest empty molecular states for nonrelativistic (on the left) and relativistic (on
the right) calculations. The states are classified by the irreps of the groups T.t and
~ (double tetragonal group), respectively.
These states are generated by 6s and 6p (Sl/2,P1/2,P3/2) states of the Bi atom.
The site symmetry of atoms in the molecule Bi4 is C 3v (C 3v ). In the molecular
field of symmetry T.t (~) the atomic 6p(P3/2) energy level is split into levels of
E leV] Fig. 5.5. One-electron energies in Bi4 for

nonrelativistic (left) and relativistic (right)
calculations [5.4]. The known energies of
occupied states are marked with black
circles
6p
-12
-24
0(3)
symmetry a l and e(eil), el2 ), e2 ). The irreps ell) and ei2 ) of the group C3v are
complex conjugate and, due to time reversal symmetry, the corresponding states
have the same energy_
Consider now the possible variants of distribution for energy levels of
occupied one-electron states into sets compatible with the existence of localized
orbitals of some symmetry. The states of symmetry al, t 2(e l ,e2,]) [for the
atomic 6s (Sl/2) states] form the basis of the group T.i (1d) rep induced by irrep
a l (e 2 ) of site group C 3v (C 3v ) (Table 4.2 and Ref [5.5]). These states of the Bi4
molecule correspond to the localized orbitals of symmetry a l (e 2 ) centered on Bi
atoms. The set of occupied states t 2 , e, a l (J, el , e2 ,]) is a basis of the group T.i
(1d) rep induced by irrep a l (e) of site group C 2v (C 2v ) related to the two-centered
Bi-Bi bond. The corresponding localized orbitals are centered on the line per-
pendicular to the Bi-Bi bond axis and passing through its midpoint. The space
coordinate part of such a localized orbital is composed of p-type functions and
has theform [ClPz + C 2 (Px + PY)]l + [C1Pz - C 2 (Px + Py )]2' C 1 and C 2 being
coefficients which are not determined by symmetry alone. The other five local-
ized orbitals of the set are generated from this one by symmetry operations of
the T.i group.
It is possible to interpret the localization of states also in another manner.
The molecular states of symmetry al' t2 due to p-states of Bi form the basis of
the induced rep (C 3v , ad. The rest of the occupied molecular states of symmetry
e in this approach are to be interpreted as the states describing a four-center
bond. As these states are obviously delocalized this interpretation seems to be
less preferable than the previous one. However, the use of the classification
scheme according to the irreps of double groups (1d, C3v ) changes the situation.
In this case there are also two possible symmetry-allowed variants. In the first
one the states]' e1 , e2 , J are considered to be the basis of the induced rep
(C 2v , e). The corresponding localized orbitals describe the two-centered bond as
in the case without spin-orbit interaction. In the second variant the states]' e1 ,
e2, J are partitioned into two sets (], e 1, e 2) and J that form the bases of induced
reps (C 3v , e2) and C3V(e~1) [or C3v(e~2)]. So these molecular orbitals may be
considered as generated by localized orbitals of symmetry e 2 and e~l) (or e~2
centered on the line with the symmetry C3v (site symmetry group of the Bi
atom).
This example shows that taking relativistic effects into account may change
the electron density localization. The study of such changes is based on the table
of double-valued induced reps of point groups [5.5].
5.3 One-Electron Approximation for Crystals
5.3.1 Crystalline Orbitals. Degenerate and Nondegenerate Energy Bands

We consider in more detail the solutions of the one-electron equation
ii<p = E<p , (5.3.1)
where <p are one-electron functions defining the crystalline orbitals. We write the
Hamiltonian for the one-electron approximation in the form
ii = -(h2j2m)L1 + V(r) . (5.3.2)
The potential V(r) includes the operator of electron interaction with the nuclei
of the crystal through (5.1.8), Coulomb J and exchange K operators (5.1.16). The
Hamiltonian ii may be an operator corresponding to the self-consistent solu-
tion of the Hartree-Fock system (5.1.20) or an operator used at the pth step of
the iteration procedure.
Both V(r) and ii are invariant under the operations of the crystal symmetry
group G or G(A), depending on the chosen model (Sect. 3.3). Further we shall use
G to denote the symmetry group of a crystal regardless of the choice of the
model (that is, infinite crystal or cyclic crystal).
According to the Wigner theorem (Sect. 3.5) eigenfunctions and eigenvalues
(one-electron energies) of the operator ii are classified by the irreps of its sym-
metry group. An irrep D(*ky) of a space group G is characterized by an irreduc-
ible star *k and by an index y distinguishing inequivalent irreps with the star *k
(Sect. 3.8). The basis vectors of the irrep D(*ky) are labeled by wave vectors
k j = gjk (j = 1,2, ... , p, gj E G) from the star *k and by the index i (i = 1,2, ... ,
ny) denoting the basis vectors of the small irrep oflittle group G kj (group of wave
vector k). The independent solutions of (5.3.1) with the same symmetry
(transforming according to the equivalent irreps of the space group G) are de-
5.3 One-Electron Approximation for Crystals 145
noted by the index 11. Thus, a one-electron function [a solution of (5.3.1)] is

specified by indexes y,k,i,J.1: ([J~~)(k,r). The functions ([J~~)(k,r) have the same
pny-fold degenerate eigenvalue of the one-electron equation (5.3.1)
(5.3.3)
As we shall see, the one-electron energies EY/l(k) [and functions <pIV(k,r)] are
continuous functions of the wave vector k (in the model of an infinite crystal).
This means that the spectrum of the operator (5.3.2) is continuous in some
energy intervals called energy bands (bands of allowed energies). For a fixed k
one-electron energy levels are ny-times degenerate. The corresponding functions
(for fixed y, j1, k) span the space of the small irrep oflittle group G".
If at any k in the Brillouin zone one-electron levels of an energy band are
not degenerate then the band is called simple (or nondegenerate). If at some k
the states form the space of an irrep D("Y) (ny 2': 2) of little group G", then ny
energy sheets touch at this point. The latter may be a symmetry point or a point
on a symmetry line in the Brillouin zone. A set of touching energy sheets form a
degenerate energy band. The bands of allowed energies may be separated from
one another by intervals of forbidden energies (forbidden energy bands). A one-
electron state is called occupied if the one-electron function is contained in the
determinant (5.1.9) representing a many-electron wave function of a system. If
for the ground state all the one-electron states of some number of energy bands
are occupied then the crystal is a dielectric or semiconductor, depending on the
width of the forbidden gap separating the highest fully occupied band from the
lowest vacant band. The upper fully occupied bands are called the valence
bands. The vacant bands are called the conduction bands. The crystals with one
or several partly occupied bands in the ground state are metals.
A clear, but not complete, image of an energy band is given by a diagram of
the energy function E(k) along various directions in the Brillouin zone. Figure
5.6 reproduces the energy bands of the crystal AgF (space group oZ,
1+~1+
3-7~:~
2-
L A r x Fig. 5.6. One-electron energy bands in AgF crystal

face-centered cubic lattice) along the directions A(FX) and A (FL). The upper
band in Fig. 5.6 is nondegenerate. The lowest band is three-fold degenerate.
Moreover, the three energy sheets touch at the F point of the Brillouin zone.
Along the A and A symmetry lines only two sheets touch and the third (the
lowest on Fig. 5.6) splits away. In crystalline AgF the two lower degenerate
bands are valence bands, the upper non degenerate one is a conduction band.
Figure 5.6 also indicates the indexes of small irreps of the oZ space group
according to which the corresponding crystalline orbitals transform in the F, X
and L points in the Brillouin zone.
5.3.2 Equivalent Hamiltonians for the Same Crystal Structures

Let H be a one-electron Hamiltonian that has the space group G as its symme-
try group. Let us suppoe that cp!;)(k,r) is an eigenfunction of H(r) with the
eigenvalue E~)(k):
(5.3.4)
where the index l' numbers the irreps of the wave vector group G".
Let go be some coordinate transformation not necessarily in G:
(5.3.5)
so that D(go)cp!;)(k, r) is an eigenfunction of the new Hamiltonian H'(r) =

D(go)H(r)D(gr/) with the same eigenvalue E~)(k). For go E G, H'(r) = H(r).
The transformation g belongs to the symmetry group G' ofthe Hamiltonian
fi'if
D(g)fi'(r)D(g-l) = H'(r) , (5.3.6)
or
(5.3.7)
or
(5.3.8)
If gr/ggo E G for every g E G the symmetry group of the Hamiltonian fi'(r) is

identical to the space group G of symmetry of the Hamiltonian H(r).
The set of transformations go that satisfy this condition form a group Ga of
automorphisms of G and G <J Ga. The number of different Hamiltonians H' that
correspond to the same physical system and which have the space group Gas
their group of symmetry is na/nG where na and nG are the orders of space groups
Ga and G, respectively [5.6]. These different Hamiltonians have identical sets of
energy eigenvalues but the symmetry labels attached to an eigenvalue of H' are,
in general, different from those attached to the same eigenvalue of fi.
As a possible realization of different Hamiltonians fi' for the same physical

system with the symmetry group G we consider different physically equivalent
Wyckoff site descriptions of the same crystal structure [5.7]. These descrip-
tions satisfy the condition go 1g gaEG for all (R Iv) = gEG and ga = (E Iva) if
(R Va - va) is a lattice translation aR associated with the space group G. In-
deed,
(5.3.9)
Let ({J~~)(k, r) satisfy (5.3.4). Then the function fj(go)({J~~)(k, r) is an
eigenfunction of the Hamiltonian fi' with the eigenvalue E~)(k) (5.3.5). For go =
(Elvo) (pure translation) fj(go)({J!~)(k, r) is a function with the same wave vector
k as ({J~~)(k, r). Indeed, for any primitive translation (Ela.) (since pure transla-
tions commute) we have
(5.3.10)
The only possible effect of translation (Elvo) is the change of the label y of the
irrep.
As an example we consider the space group Dlt. In [5.7] the allowed per-
mutations of the Wyckoff sites for this space group are found: a +-+ b; g +-+ f.
If Va = rb-ra = (D,O,el2), the symmetry operation R of the point group D4h
gives the vector R va - va = aR (aR = D or - a3 depending on the point group
operation R). Thus the operation g = (R IV)EG is mapped by the operation
g' = (Rlv+aR)EG'(G +-+ G').
5.3.3 k - p Perturbation Method in the Energy Band Theory

The set of discrete indexes y, i, J1 can be combined in a single index s: ({Js(k, r),
Es(k). In the sequence of eigenvalues Es(k) numbered in such a way, each is
repeated as many times as the degree of its degeneracy (for fixed k). Obviously
Es(gk) = Es(k) , gEG. (5.3.11)
The functions ({Js(k, r) form a complete orthonormal system

{Js(k,r), ({Js,(k',r)) = J({Js+ (k,r) ({Js,(k,r)dr = 0ss,o(k-k') (5.3.12)
They transform according to irreps of the translation group T and are called
Bloch functions
i.fPs(k, r) = exp( - ik a,.)fPs(k, r) (5.3.13)
and may be written in the form
fPs(k, r) = exp(ik r) Us(k, r) , (5.3.14)
where Us(k,r) are periodic (in direct lattice) functions

Us(k, r + aJ = U,(k, r) , (5.3.15)

a i (i= 1,2,3) being primitive lattice vectors.
We consider in more detail the integral (5.3.12). Let us partition the space
into unit cells of volume v" (Sect. 3.3.1) and make the substitution in the nth unit
cell r = p + a . Using (5.3.13) we have
JJs*(k, r)Js,(k', r) dr = L exp( -i(k -

k')' a.) J J:(k,p)Js,(k',p) dp
Va
= 2n?Iv,,) J J:(k,p)Js,(k,p)dpb(k -
Va
k')
= 2n)3/v,,) J U:(k,r)Us,(k,r)drb(k - k') . (5.3.16)

Va
Comparing (5.3.16) and (5.3.12) we see that the functions Js(k,r) and Vs(k, r) (for
fixed k) satisfy the following orthonormalization condition:
2n?Iv,,) J J:(k,r)Js,(k,r)dr = 2n)3/v,,) J U:(k,r)Us,(k,r)dr

Va Va
= bss ' . (5.3.17)
The functions Us(k, r) for fixed k form a complete orthonormal set in the
space of periodic functions (with periods ai ).The functions exp(ik . r) Us(k, r) also
form an orthonormal set which is complete in the space of functions
transforming according to the kth irrep of the translation group T. In this space
the set of functions
ifis(k, r) = exp(ik r) Us(k o, r) = exp(ix' r)Js(k o, r) (5.3.18)
where x = k - ko is also complete. The set of functions in (5.3.18) is also

orthonormal
2n)3 Iv,,) J ifi:(k, r)ifis,(k, r) dr = 2n)3 Iv,,) J J:(k o, r) Js' (k o, r) dr

Va Va
= bss' . (5.3.19)
We shall consider the functions Js(k o, r) [and therefore ifis(k, r)] to be known.
For the solution of the one-electron equation
Ii J,(k, r) = Es(k) Js(k, r) (5.3.20)
let us express the function Js(k, r) in the form of an expansion over the complete
set ifis(k, r)
Js(k, r) = Ls' Cs' ifis,(k, r) . (5.3.21)
Substituting (5.3.21) into (5.3.20), multiplying by (2n)3 Iv,,) ifi:(k r), integrating
over the unit cell volume v" and using (5.3.19), we shall get, after simple transfor-
mations, the system of equations for the coefficients Cs equivalent to (5.3.20)
Ls' ([Es(k o) + h2 x 2 /2m - Es(k)]c5ss' + hx'pss,/m}Cs' = 0 , (5.3.22)
where
(5.3.23)
and p = - ihV is the momentum operator.

Let x = k - ko be small. To solve (5.3.22) we apply a perturbation method.
We see from (5.3.22) that the equations for one-electron energies Es(k) at the
point k differ only by small terms hx .Pss' /m and h 2 x 2 /2m from the equations for
energies Es(k o) at a neighboring point ko = k - x. So we see that small varia-
tions of wave vector k cause small variations in energies Es(k). As k is an arbi-
trary point in the Brillouin zone this means that Es(k) are continuous functions
of the wave vector for all k in the Brillouin zone.
Let a one-electron level Es(k o) be ny-fold degenerate and the corresponding
functions
i = 1, 2, ... , ny , (5.3.24)
span the space of an irrep D(koY) of G ko ' The first order (with respect to x)
corrections to an energy level Es(k o) and the "correct" zero order functions are
found as a solution of the linear system
L (hx' pss)m)C!?) = E(l)C!O) . (5.3.25)

s'
A nonzero solution of this system exists if the determinant of the system is equal
to zero
(5.3.26)
The determinant in (5.3.26) is a polynomial of degree ny with respect to E(1).
Equation (5.3.26) has ny roots
i = 1, 2, ... ,ny . (5.3.27)
All roots depend linearly on the components of the vector x. There may be equal
values among the EP)(x). So the ny-fold degenerate energy level Es(k o) splits up
into components. Some of them remain degenerate. The number of components
and their remaining degeneracy are determined as follows, Initially we know
that the states at the point k = ko + x transform according to irreps of the little
group Gk' If G k +-+ G ko there is no splitting when ko moves to k. The energy level
and the corresponding wave functions of symmetry y (irrep D(k Y) in the point
O
ko smoothly transform into the energy level and the wave functions of symmetry
y (irrep D(k y) in the point k = ko + x. If Gk e G ko then an analogous continuity
takes place, the classification in both points being according to irreps of the
common symmetry group G k. We denote formally by Dt~)ko the irreps of G k
with k equal to k o' Decompose the restriction of the irreps of G ko on the
elements of G k (with k = k o ) into irreps of G k
(5.3.28)
It is obvious that when k moves from ko the energy level Es(k o) splits up into
sublevels whose number is equal to the number La
r~Y) of the group Gk(k = k o )
irreps contained in the irrep D(koY) of Gko
r~Y) = ni/ L (Xt~)ko(g))*X<kOY)(g) , g=(Rlv) . (5.3.29)

ReF.
The degeneracies of sublevels are determined by the dimensions na of small

irreps Dt~)ko of the little group Gk'
Thus the symmetry of states in less symmetrical points of the Brillouin zone
for any energy band can be uniquely determined by the symmetry of states in
more symmetrical points. This connection (called the compatibility relation)
arises only from symmetry considerations and does not depend on the particu-
lar features of the one-electron Hamiltonian (see Sect. 3.8.6). To establish the
compatibility relations over all the Brillouin zone it is sufficient to know the
characters of wave vector group irreps for the representatives (R I v) (REFk ) of
co sets into the decompositions of Ok with respect to translation subgroup T.
Note that the characters in (5.3.29) may be substituted by the characters of
projective irreps of point groups Fk connected by simple relations with small
irreps of Ok (Sect. 3.8.3).
Because the correction E(l) in (5.3.25) is proportional to Xi (i = 1,2,3), after
dividing both parts of the equations (5.3.25) by X we have the equations for the
"correct" zero order functions. Therefore the coefficients C!O) (zero order
functions) satisfying the system (5.3.25) depend on the direction of the vector x.
When a point k moves to a point ko along different directions on an energy
sheet, we have, in the case ofa degenerate band, different wave functions (5.3.21)
at ko [different linear combinations of the basis functions <p,(ko, r)]. This means
that the energy sheets having the same energy at the point ko are coupled and
cannot be considered as ny independent energy sheets touching only at the point
k o. It is impossible to pick out from the set a sheet where the wave function
would be a single-valued and continuous function of the wave vector at the
point k o.
5.3.4 Zero-Slope Points of Energy Bands

The first-order corrections E(1) may be equal to zero. This occurs when all the
values Pss' = O. Let us consider in more detail the 3n; values (i = 1,2,3)
(5.3.30)
We determine the symmetry properties of the integrand

cPss,(r) = cp:(k o, r)picps,(ko, r) (5.3.31)
under the elements of the group Gko ' The operators pi are invariant under
translations, i.e., they transform according to the vector rep D(v) with k = 0 of
Gko ' The group Gko as a space group has the irreps with all the possible k-
vectors in the Brillouin zone, in particular, it has the irreps with k = 0 which are
not allowed (small) irreps for ko #- O. The product cp:(k o, r) x <i>s,(ko, r)
transforms also according to some rep of Gko with k = O. The total integrand in
(5.3.31) transforms according to the rep
(5.3.32)
of Gko with k = O.
In the set of 3n; integrals (5.3.30) the number of independent, nonzero,
integrals is equal to the multiplicity of the identity irrep in the direct product of
reps (5.3.32)
g = (Rlv) . (5.3.33)
If r 1 = 0 then the first order corrections are equal to zero. In this case the point
ko is called a zero-slope point, (oE/ox i = 0). If the irrep is one-dimensional
(nondegenerate at the point k o), then IX(kOY)I Z = 1, i.e., (D(k oY)* x D(koY) is the
identity irrep of the group Gko ' In this case the number of nonzero independent
integrals is equal to the number of identity irreps contained in the vector rep of
the group Gko
(5.3.34)
If r 1 = 0, the nondegenerate band has a zero slope at the point k o.

As an example consider again the energy bands in crystalline AgF. For the
r point (k = 0), Fr = 0h' For the state y = r4- = t 1u (the irrep t 1u is a vector
irrep in the group 0h) r 1 = O. All three sheets of this band have a zero slope at
the point k = 0 in any direction.
Analysis of the upper nondegenerate band gives the following results:
1) The point r; Fr = 0h' The rep v = t 1u is itself irreducible and does not
contain the identity irrep. All three integrals (5.3.30) are equal to zero. The
point r is a zero-slope point.
2) The point X(2n/a,OO). Fx = D4h ; v = azu + eu ' The point X is a zero-slope
point.
3) The point L(n/a, n/a, n/a). FL = D3d ; v = azu + eu ' The point L is a zero-
slope point.
4) A point on the symmetry line L/(x, 0, 0). F,j = C4v , V = a 1 + e.
pis = P:s = 0 .
5) A point on the symmetry line A(x, x, x). FA = C 3v , V = a1 + e.

P:' + pis + P;s =I- 0 .
At all points on the symmetry line LI(x, 0, 0), iJE/iJxy = iJE/iJx z = 0 due to
symmetry considerations. The vaue of the derivative iJE/iJx x along the direction
LI depends on the actual behavior of the integrand (5.3.31) and, as is seen from
Fig. 5.6, at some point Llo is equal to zero. Analogous results may be obtained
for the direction A(x, x, x).
5.3.5 Energy Bands in the Neighborhood of Degeneracy Points

If the first order corrections are equal to zero (at zero-slope points), then the
second order corrections with respect to components Xi and the coefficients qO)
are determined from the system of equations
L (Hss' - E(2)(jss')C!~) = 0 , (5.3.35)

s'
where
H . = (1i2/2m) '\' [ m- 1 '\'

ij+ji
PsnPns' PsnPns' + (j .(j..
]
.. (5.3.36)
L L E (k ) _ E (k) x,x} ,

ss ss '}
ij n #s sOn
S, S' = 1,2, ... , ny .

The second order corrections E(2) are the roots of the equation
(5.3.37)
The part of the matrix H that is a multiple of the unit matrix causes a common
shift of all the roots of the equation (5.3.37). Let us analyze the remaining part
of the matrix H. Consider those members of the sum in (5.3.36) where the index
n labels the states spanning the space of the same irrep D(koY) of the little group
Gko ' They have the same energy denominators. Let us write the sum
L (P;nP~s' + P!nP!s')
n
(5.3.38)
as one integral over the variables rand r' from the integrand
cP;~. = L [<p!y)(k o, r)<p~(J>(ko, r')] *p ij x <p~(J>(ko, r) <p!Y)(ko , r') . (5.3.39)

n
The function (5.3.39) is periodic (with periods a i over rand r'). It transforms
according to some rep with k = 0 of the group Gko (this is not an allowed rep of
GkJ The operator
transforms according to the symmetrical square of the vector rep of Gko (Sect.
2.3.1). We denote it by [D(v)]2. Apply the operator gk o (gko E Gko is a representa-
tive of any coset in the decomposition of Gko with respect to the translation
group) to the function (5.3.39)
di.ij
gko 'P'ss'
A =" " " " (D(Y)D(P))* [D(V)]?
~ ~ ~ ~ ps n'n
..D(P)
l'/l}
D(Y)
n"n p's'
X (m(Y)m(~))*pi'j' m(~)m(~)
""p 't'n 't'n "t'p
n n'n" pp' i' j'
(5.3.41)
But
L (D!~~(g))* D!~~(g) = L D!~~(g)D!~!(g-l) = <5n"n'

n
(5.3.42)
Therefore
gkOcf>;~, = L (D~~)*[D(V)]?-j'ijD~~~,cf>~t: (5.3.43)

i'j'pp'
The function (5.3.39) transforms according to the rep (with k = 0)
(D(Y))* X [D(V)]2 x D(Y) (5.3.44)
of the group Gko ' This result does not depend on the symmetry (rep D(P)) of the
functions ({J!P)(k o, r) contained in cf>;~,. Each partial sum in (5.3.38), and conse-
quently the sum over n in (5.3.36), is not equal to zero only if the rep (5.3.44) of
Gko contains the unit irrep. The number of independent elements of the matrix
Hss ' in (5.3.36) equals the multiplicity of the unit irrep in the rep (5.3.44):
(5.3.45)
If D(Y) is a one-dimensional irrep (i.e., the band is nondegenerate at the point

ko), then the rep (D(Y))* x D(Y) is a unit rep and Ix(Y)(gW = 1. Then, instead of
(5.3.45) we have
(5.3.46)
Consider again as an example the energy bands shown in Fig. 5.6. For the
lowest band the point r is a zero-slope point. According to (5.3.45), for the rep
(5.3.44) '1 = 3 (v = y = r 4- = tlu)' Take as independent parameters the
quantities
A = h2/2m + (h 2/m 2) L IP:nI 2/(E - En) ;

n
B = h2/2m + (h 2 /m 2) L IP~nI2/(E - En) ; (5.3.47)

n
C= L (P:nP~y + P~nP:y)/(E -
n
En)
(subscripts x, y, z on the momentum operator label the states spanning the irrep
F 4- space). The matrix H takes the form
[ AX~ +CXxXy
B(x; + x;)
Ax;
CXxXy
+ B(x~ + x;)
CXxx z
CXyX Z
1
(5.3.48)
Cxxx z CXyX Z Ax; + B(x~ + x;)
The roots of(5.3.37) with the matrix (5.3.48) give the energy levels in the domain
of small xx, x y, Xz near the top of the three-fold band. The constants A, B, C may
be either calculated according to (5.3.47) or found with the help of experimental
data (e.g., optical spectra). If a band is nondegenerate at a zero-slope point,
(5.3.36) gives directly for energy levels at small x
Es(k o + x) = Es(k o) + L (h2/2)(1/m)ijxixj + ...

ij
(5.3.49)
The set of values
(5.3.50)
is called the symmetrical reverse effective mass tensor. On reducing the tensor to
the main axes, the expression for energy levels takes the form
Es(k o + x) = Es(k o) + L (h2/2mJx; , (5.3.51)

i
where the index i denotes the components of the vector along the main axes of
the reverse effective mass tensor.
In the case of the nondegenerate band in the AgF crystal (Fig. 5.6) we find
the following results for the F, X, and L points in the Brillouin zone. According
to (5.3.46) there is only one independent parameter in the reverse effective mass
tensor. It is easy to see that
l/m* = l/mx = l/my = l/m z
(5.3.52)
The energy near k = 0 is approximated by
(5.3.53)
The surfaces of constant energy are spheres in the neighborhood of k = 0 (F-

point).
At the point X the little point group is Fx = D4h . According to (5.3.46) the
tensor of reverse effective mass has two independent components. Energy levels
depend on the components of the vector x as
(5.3.54)
where mil and ml. are longitudinal and transverse effective masses. The surface of
constant energy (at small x) is an ellipsoid of revolution about the (100) direc-
tion. The dispersion law (energy dependence on the components of the x-vector)
near two other points in th Brillouin zone from the star of wave vector kx [on
the directions (010) and (001)] is analogous. This type of band structure is called
many-ellipsoidal or many-valleyed.
The little group of the point L is FL = D3d At this point there are also two
effective masses (longitudinal and transverse) and the dispersion law is analo-
gous to (5.3.54) but with the ellipsoid of revolution now oriented along the (111)
direction. The star *k L consists of four vectors. Hence there will be four such
ellipsoids as surfaces of constant energy.
5.3.6 Additional Degeneracy of Energy Bands Due to the Reality

of the Hamiltonian
In application to space groups the criteria (2.2.49) of the reality of an irrep has
the following form:
1, if D(*k,a) is real (1),
0, if D(*k,a) and (D(*k,a*
{
(nslnF) L X(k,a)R IV)2) = ~re i~equi~alent. (2),
Rk= -k+Bm -1, If D( k,a) IS eqUIvalent to
(D(*k,a * but not real (3),
where ns is the number of k vectors in the star *k; nF is the order of the
crystal point group F and X(k,a) is the character of a small irrep of the wave
vector group G k ; the sum is over REFk which transform the wave vector k in-
to -k or its equivalent (see also Sect. 9.3).
Let q>!Y)(kj , r) (s = 1,2, ... , ny,j = 1,2, ... , p) be eigenfunctions of the one-electron
real Hamiltonian of a crystal with eigenvalues E(k 1 ) = E(k2) = ... = E(k p ) and
spanning the space of an irrep D(*/cY) of space group G. The functions (q>!Y)(kj , r*
transform under translations according to the irreps k; = - k j of the translation
group T and form the basis of irrep D(*/c'Y) = (D(*/cY* of G. If the stars *k and
*k' do not coincide, i.e., the vectors k j and - k j are not in the same star, then the
irrep D(*/cY) and D(*/c'Y) are not equivalent and an additional degeneracy of energy
levels arises (Sect. 3.5.3, case 2)
(5.3.55)
Thus the symmetry relation (5.3.55) is fulfilled for all points k in the Brillouin
zone and for all space groups. If the vectors k j and - k j are members of the same
irreducible star, then the symmetry relation (5.3.55) is a consequence of space
symmetry. If the vectors k j and -kj belong to different stars, (5.3.55) is due to
the Hamiltonian being real.
When k and - k belong to the same irreducible star the degeneracy is

doubled at every k from the star, if the rep D(*ley) is nonequivalent to (D(*/cY)* or
equivalent to (D(*ley)* but is not real (Sect. 3.5.3, cases 2 and 3). In these cases
the functions cp!Y) (kj' r) and (cp!y)( - kj' r))* (8 = 1,2, ... , ny) correspond to the
same wave vector k j and are linearly independent.
5.3.7 Density of States ofan Energy Band

The density of states g(e) is one of the important features of the crystal band
structure. The value g(e) de is equal to the number of states in an energy band
with energies within the interval from e to e + de. In the model of an infinite
crystal this number seems to be infinite since the wave vector varies continuous-
ly. We shall consider the density of states in the model of a finite but boundless
crystal (cyclic system, Sect. 3.3.2), where the wave vector takes a finite number of
values, although the set of these values is very dense for a cyclic system of
macroscopically large size. The cyclic model takes into account one of the im-
portant features of a real crystal, namely, the finiteness of its dimensions, which
causes the discrete nature of states and therefore the finite number of states in
any energy interval.
For a fixed self-consistent potential in (5.3.1) one-electron energy levels and
the corresponding states coincide in both models at the set of k E K (Sect. 5.5.2)
[5.8]. Thus the band structure in the cyclic model reproduces the band structure
in the model of an infinite crystal in the discrete set K of k-points. The details of
the behavior of Es(k) and CPs(k, r) as functions of the wave vector k are
manifested in regions of k-space considerably exceeding the distance between
nearest points of the set K (which is of the order of Bjj"i). That is why in the
cyclic crystal model the energy levels Es(k) and the wave functions cp.(k, r) can be
considered as functions of a continuous (quasi-continuous) variable k. At the
same time it is easy to take into account the finiteness of the number of states in
a band, which is proportional to the number of points in the set K uniformly
distributed over the Brillouin zone. The volume (2n)3 jv" of the Brillouin zone is
occupied by L points of the set K (L is also equal to the number of unit cells in
the cyclic model). Therefore, the number of states in the volume dk is equal to
Lv" dkj(2n)3 = V dkj(2n)3 where V is the volume of the crystal. For any function
P(k) of the quasi-continuous wave vector k the sum over the points of the set K
can be replaced by the integral over the Brillouin zone,
L P(k) = Vj(2n)3 JP(k)dk . (5.3.56)

lEK
Consider the case of a nondegenerate energy band. Let E(k) = e and E(k) =
e + de be two neighboring surfaces of equal energy. The number of points of the
set K between them is equal to g(e) de. According to (5.3.56) for P(k) = 1
g(e) de = L 1 = Vj(2n)3 Jdk
Ie
, (5.3.57)
where the integration is over the space between the surfaces of equal energies.
Write the small volume element dk in the form
dk = dsJk , (5.3.58)
where ds is an element of constant energy surface area E(k) = sand Jk is the
thickness of the layer measured along the perpendicular to the surfaces. Since
the vector VE(k) is perpendicular to the surface E(k) = s,
E(k + Jk) = E(k) + I VE(k) IJk = s + ds (5.3.59)

and
Jk = ds/I VE(k)1 . (5.3.60)
Substituting (5.3.58) and (5.3.60) into (5.3.57) and dividing by ds we get
g(s) = (2n)3
v f WE(k)I'
ds (5.3.61)
where the integration is over the surface of constant energy E(k) = s. In the
points of the Brillouin zone where I VE(k) I = 0 the integrand has a singularity,
which may cause a peculiarity in the behavior of the function g(s) at this energy.
These are local extrema or saddle points of the function E(k). Near the bottom
of a band at a point ko the energy function E(k) has the form (in the coordinates
of the main axes of the reverse effective mass tensor)
E(k) = E(k o) + (h 2/2) L (k i - koY/mi . (5.3.62)

i
In terms of Xi = h(ki - koJ/ jm; the surfaces of equal energies

E(k) = sex) = So + x2/2 (5.3.63)
are spheres. According to (5.3.57)
g(s) ds = J
(VJ m 1 m2 m3/(2nh)3) dx 1 dX 2 dX3
= (VJmlm2m3/(2nh)3)4J21t~ds . (5.3.64)
If the star of the vector ko consists of p rays there are p equivalent minima in an
energy band and the density of states must be multiplied by p. Hence near the
bottom of the band the density of states is
O, s < eo ,
g ()
e = { (5.3.65)
[VpJmlm2m3/(2nh)3]4J2n~, e > eo .
Analogous calculations for the top of a band at the point ko
E(k) = E(k o) - (h 2/2) L (k i -

i
koY/m i
(5.3.66)
g(e) Fig. 5.7. Van Hove singularities of band densities of states

(in three dimensions) shown by the arrows
~L- __________ L-~e
(5.3.67)
Figure 5.7 represents schematically the main features of the function g(8)
near the top and the bottom of a band and near the saddle points. The latter
may be of two types according to the number of minus signs before the qua-
dratic terms x 2 in the energy function. In the case of three-dimensional
triperiodic structures there may be no other singularities. They are called Van
Hove singularities.
5.4 Induced Representations and the Theory

of Chemical Bonding in Crystals
5.4.1 Energy Band States and Localized Functions
The Bloch functions o/!;)(k, r) of a crystal determine the electronic charge distri-
bution in the direct space and hence determine the nature of chemical bonds in
a crystal. Quantum mechanical calculations of electronic structure have been
made for a large number of solids, using different methods of electron band
theory [5.9]. The one-electron functions obtained can be used to study the
physical and chemical properties of crystals. The Bloch functions o/!;)(k, r) con-
tain, in principle, all the necessary information about these properties. But some
properties of solids can be better understood in terms of localized (Wannier)
functions. Their use allows one to connect the structure and properties of solids
with those of related molecules more easy, to explain the additivity of some
properties of crystals with respect to separate chemical bonds and the trends in
some properties of related crystalline compounds.
The localized functions are linear combinations [(4.2.10); Sect. 5.5.1] of
delocalized Bloch functions-eigenfunctions of the Hamiltonian H of a crystal,
related to a given energy band and forming the space of a band rep of the
symmetry group G of the Hamiltonian H. The theory of induced reps of space
groups gives the answer to the question of whether it is possible to generate in
the space of states of a given energy band the basis of localized functions? The
answer is affirmative if the band rep is a simple induced rep or the sum of simple
induced reps. Otherwise the answer is negative. Moreover, the induced rep
theory allows one to determine the positions of symmetry localization centers
5.4 Induced Representations and the Theory of Chemical Bonding in Crystals 159
and the symmetry properties of localized functions, although this determination

is not always unique.
The index of a simple induced rep in the k-basis in almost all cases uniquely
defines its index in the q-basis. Therefore we get, unambiguously, the Wyckoff
positions and the irreps of the corresponding site symmetry groups which char-
acterize the location and the symmetry properties of localized functions related
to the energy band under consideration. But, as is shown in [5.10] for 14 space
groups (Di,D~~,D~t,D~,D!O,D~d,DU,D~, T2, T4, 0 3 , 0 4 , 0 6 , 0 7 ,0 8 ), there are
pairs of different Wyckoff sets which generate equivalent simple induced reps. In
this case we have two possible choices of the centers of localization of the
Wannier functions. From symmetry considerations the two possibilities are
identical, and it is necessary to take into account the particular details of the
behavior of the Bloch functions to choose the correct centers of localization.
Let an induced rep be composite. As we know, the decomposition of a
composite induced rep into simple ones is not always unique. If it is unique the
center of localization and symmetry properties of the localized functions are
determined by the indexes of the simple induced reps in the decomposition. It
may happen, however, that the composite induced rep in question has two or
more decompositions into simple ones. In particular this is the case when a site
symmetry group Gil of a q-point is a subgroup of several different site groups Gil'
of points q'EQ (see Sect. 4.2.3). In this case, symmetry considerations alone
do not allow one to unequivocally determine the point of localization and sym-
metry properties of localized functions corresponding to the composite energy
band. In any case the induced rep theory may point out all the possible
variants. First there are the variants where these features of localized functions
are indicated by the indexes of the simple induced rep in the decomposition
mentioned above. There are also possible variants with the centers of localiza-
tion q$Q. The number of energy sheets in a composite band is equal to the
number of the localized functions centered in the unit cell (p = nqnp), i.e., is
a multiple of nq = nF/nO' This consideration permits one to choose the
points q which according to this criterion correspond to the composite induced
rep in question. Then one has to analyze the reps of the space group G induced
by the irreps of dimension np of the site group G q of the point q, chosen as
described earlier.
All the possibilities mentioned are symmetry equivalent. The best variant is
that which assures the best possible localization ofWannier functions according
to some additional criterion. The latter depends on the actual behavior of the
Bloch states of the energy band. The number of possibilities increases for the
space groups indicated in [5.10] (Sect. 4.2.3) where there are pairs of equivalent
reps induced from irreps of maximal isotropy subgroups.
5.4.2 Localized Orbitals and Atomic States in Crystals

The following qualitative discussion should explain some features of band reps
corresponding to real energy bands in crystals. Let a crystal be formed from
isolated constituent atoms by decreasing the interatomic distances from very

large ones to those corresponding to real crystalline structure. The crystal field
may split the degenerate one-electron atomic levels due to symmetry require-
ments, leading to quite narrow energy bands, because of the interatomic interac-
tions. The interatomic distances are sufficiently large that the Wannier functions
corresponding to these bands are localized quite well at the atomic sites and are
close to atomic functions. The Bloch states of these narrow energy bands span
the spaces of some band reps which certainly have q-bases, i.e., are induced
representations. These reps are induced by those irreps of site symmetry groups
of atoms which describe the transformation properties of atomic states
generating the energy bands. The further decrease of the interatomic distances
may considerably transform the energy bands (join them together into more
complicated ones and later split them up again into other simple ones) but a
new electronic state of arbitrary symmetry cannot arise nor can any state disap-
pear. At the same time, the wave functions of all possible symmetry types may
change and corresponding one-electron energies may shift along the energy
scale. Thus an energy band corresponding to a band rep without a q-basis (i.e.,
which is not an induced rep) may arise. However, this band, in joining with one
or several neighboring ones, forms an energy band corresponding to a compos-
ite induced rep with a q-basis. In the joint space of these band states one can
generate the basis of localized functions. Thus the calculated one-electron en-
ergy band spectra of crystals may always be divided into bands connected with
some simple or composite induced reps.
When the interatomic distances are decreased to those in a real crystal the
atomic functions undergo more or less extensive modifications and become the
Wannier functions of a crystal. When the latter arise directly from atomic
functions one can use for them the same notation (s, p, d and so on).
Let the atoms be at Wyckoff positions with the site summetry group Gf .
Localized functions transforming according to irreps of the group Gf corre-
spond to the bands arising from atomic levels split by a crystalline field. If these
Wyckoff positions belong to the set Q the band states usually form the space of
a simple induced rep. There are some exceptions (Sect. 4.2.3) [5.10].
When atoms are at positions which do not belong to the set Q the band
states form the basis of a composite induced rep. If when the interatomic dis-
tances are decreased the energy bands cross one another then the states of the
arising composite band also span the space of a composite induced rep. How-
ever, it may happen that this new band for further decreases in the interatomic
distances splits into several subbands related to localized functions which have
centers of localization somewhat displaced from the atomic positions. This case
is typical for the electronic structure of crystals with covalent chemical bonding.
5.4.3 Hybridized Orbitals in Crystals

Hybridized orbitals in crystals may be generated in the same way as for mole-
cules (Sect. 5.2.1). However, the atoms forming two-centered bonds in crystals
may have isomorphous site groups. Because a site symmetry group of a bond
may be the site group of any Wyckoff position in a crystal, the list of possible
site groups in crystals is larger than that in molecules.
For example, in diamond, carbon atoms occupy the Wyckoff position a
(Ga = 1d) and the site symmetry group of the C-C bond is D 3d A construc-
tion analogous to that of Sect. S.2.2 also gives the hybridized orbitals like
(S.2.16, 19).
5.4.4 Crystals with Space Group ol

In this and the following subsections we shall analyze the band structure of
some crystals using the induced rep theory. Unfortunately, information about
band energies for some symmetry points k in the Brillouin zone (in particular,
for points W in crystals with point symmetry Oh' 0, 1d and face-centered cubic
Bravais lattices) is often lacking in published results of energy band calculations.
The advantage of the symmetry analysis we are considering here is the possibil-
ity of relating the energy band states to the localized atomic-type functions even
when atomic functions are not used as the basis in the band structure calcula-
tions.
Crystals with Diamond Structure. Figure S.8 presents the energy bands in
diamond and gray tin crystals [S.11]. In both crystals the atoms (two atoms per
unit cell) occupy the Wyckoff position a with the site symmetry T.t. In diamond,
the lower conduction band and the upper valence band have the symmetry
described by the induced reps c(a zu ) and c(a 1g ) respectively (Fig. S.8 and Table
4.8). The localized functions corresponding to these induced reps are centered
in the middle of the C-C bond (Wyckoff position c), but transform according to
different irreps of the site symmetry group D 3d The basis functions of the irreps
azu and a1g of the point group D3d may be generated with the help of Sp3_
hybridized orbitals of carbon atoms (anti bonding and bonding orbitals, respec-
tively). It is precisely these hybridized orbitals which are used in the study of the
electron structure of tetrahedral crystals.
(a) (b)
2- 4
~;
2- 2
3+ : 2
3+
1+
~ ::
1+
3- 3- 2
1+ 1+
2-
2-
l [' X W l [' X W
Fig. 5.8. One-electron energy bands in diamond (a) and gray tin (b) crystals
162 5. Application oflnduced Representations
In gray tin crystals the bands c(a 2 J and c(a 19 ) come into contact with one
another at the point r(k = 0) and form one degenerate band composed of eight
energy sheets. Its symmetry is characterized by a composite induced rep
c(a 2u + a lg ) = e(ad = a(a 1 + t 2 ) = b(a l + t 2 ) (Table 4.8). Only half the states
in this band are occupied by electrons. This feature of the gray tin band struc-
ture causes the delocalization of the electron density and explains the metallic
properties of this crystal.
Cubic Si0 2 Crystal. In the fJ-cristobalite modification of silicon dioxide,
silicon atoms occupy the Wyckoff positions a with site symmetry 1d and oxygen
atoms are in Wyckoff positions c with site symmetry D3d The upper valence
bands of the crystals have the symmetry c(eJ, c(a2u) and c(a l9 ). These bands
come from sand p atomic states. The three-fold degenerate atomic p-Ievel is
split by the crystal field with symmetry D3d into sublevels a 2u and eu , which
generate the two upper valence bands of the Si0 2 crystal.
5.4.5 Crystals with Space Group O~

CaO Crystal. In calcium oxide the calcium atoms are in a positions (Ga = 0h);
the oxygen atoms are in b positions (G b = 0h). The band structure calculation
[5.12] (Fig. 5.9) leads to the following interpretation. The states of the upper-
most three-fold degenerate valence band form the basis of the simple induced
rep beth). The localized functions corresponding to this band have the same
symmetry as the oxygen 2p atomic functions (their irrep flu of the site group
G b = 0h)' The energy bands of b(al g ) and a(tlu) types are lower in energy.
The corresponding localized wave functions have the symmetry of 2s oxygen
and 3p calcium atomic functions, respectively.
The Silver Halides. The halide and silver ions in an NaCl-type structure are
at the Wyckoff positions a and b, respectively. We use the results of the band
structure calculation of [5.12] not containing the energies for the W symmetry
point. For the AgF crystal the two uppermost valence energy bands correspond
to the induced reps b(e g ) + b(t 2g ) = b(e g + t 2g ) and a(t lu ), respectively (Fig.
5.lOa). These are the atomic d-orbitals which transform according to the irreps
3+ --~---
5-
1+
2-~1+
Fig. 5.9. Valence one-electron energy bands and their induced

L r x representations in the CaO crystal
(a) (b) (c)
~~
5+
5+- 1+
~~
3-
3- 4+
2- 1+ 2- 5-
2+ 2+
3- 5- 1+
::~
4+ 5+
3- 5+ 4+
3-~5-
4- 2- 3- 2+
2- 3-
3-
2-
L r X L r X L r X
Fig.S.10. Valence one-electron energy bands and their induced representations in AgF (a), AgCl (b),
and AgBr (c) crystals
eg and t 2g of the site symmetry group Gb = Oh' so that from the symmetry point
of view the energy band b(e g + t 2g ) is related to the d-type states of the Ag atom.
However, the real localized wave functions corresponding -to this band may
differ significantly from the atomic d-type functions. The localized orbitals of the
a( t 1 J- type energy band have the symmetry of the halide atom 2p states.
In AgCl crystal two energy bands of b(e g + t 2g ) and a(t IJ type join into one
eight-fold band (Fig. 5.10b). This band is related to the composite induced rep
b(e g + t 2g ) + a(tIJ. The corresponding localized functions may be divided into
two groups. Five of them are centered at the Ag site b and have the symmetry of
an atomic d-function; the other three are centered at the halide site a and have
the symmetry of the halide atom p-functions.
In the AgBr crystal there are again two valence energy bands separated in
energy (Fig. 5.10c); we do not know the behavior of the energy band along the
line X - w- L. However, they have to be considered jointly as it is possible to
find localized wave functions related to the entire eight-fold energy band, but
not with each of the two subbands separately.
The Fluorite Crystal CaF 2' The Ca atom is at the position a (Ga = 0h); F
atoms are at the positions c (Gc = T.J). Comparing the labels of the simple in-
duced reps of the space group O~ (Table 4.7) with the results (Fig. 5.11) of the
fluorite crystal band structure calculations [5.13] one obtains the following
symmetry properties of the valence band localized functions (in decreasing
order of energy): for the band C(t2) - the symmetry of the anionic 2p-atomic
functions; for the band a(t lu) - the symmetry of the cationic 3p-atomic functons;
for the band c(ad - the symmetry of the anionic 2s-atomic functions; for the
band a(a lg ) - the symmetry of the cationic 3s-atomic functions.
5.4.6 Crystals with Space Group Di~

In Chaps. 3 and 4 we discussed the space group Di~, its reps and the crystal
structures compatible with this group. Figure 5.12 presents the calculated upper
Fig. 5.11. Valence one-electron energy bands and their induced

representations in the fluorite crystal CaP2
1+ ______2-
~. _____ ~ 4+
2- _ 3-
1+_ _ _-
1+ ..._ _ _ _ 1+
L r x
3+
1
2
3
1
4
2
2
3
2
2 1~5-
:Z5:
4+
2 5-2 4 5-
1
- ::1 31 I m 2-3- Fig. 5.12. Uppermost valence one-
2 3-,5- , 5-
electron energy bands in titanium di-
X r z r M oxide Ti0 2
valence one-electron energy bands in titanium dioxide crystal [5.14]. The sym-
metry notations of Bloch states with kEf( are also given in the figure (no infor-
mation about the energy levels and corresponding electronic state symmetries at
points A and R of the Brillouin zone is given in [5.14]). As is seen in Fig. 5.12
there are three energy bands in crystalline Ti0 2 that are separated by gaps from
other energy bands as well as from each other. Comparing the symmetry nota-
tions of these energy bands with the symbols in the k-basis of the simple induced
reps of the space group D it
(Table 4.5) one finds that they are related
to induced reps in (in order of increasing energy) which have the following
notations in the q-basis:
(5.4.1)
(5.4.2)
a(ag + b 3u + b2g + b lu + bIg + b 2u )

= b(ag + b 3u + b 2g + b lu + bIg + b 2u ) =!(al + b 1+ b 2) . (5.4.3)
The first energy band is generated by p-states of Ti atoms since they transform
according to irreps b Iu , b 2u and b 3u of the site symmetry group D2h of the
Wyckoff position a occupied by Ti atoms (Table 4.5).
Using the procedure described in Sect. 4.5.1 it is easily shown that the sec-
ond energy band which has the index given by (5.4.2) is generated by s-states
of oxygen atoms and has also the notation !(al) in the q-basis. In the same
way we find for the uppermost valence band (5.4.3) in the q-basis the notation
f(al + b l + b2). It is generated by p-states of oxygen atoms.
Hence the localized functions of uppermost valence bands responsible for
chemical bonding are centered on atoms and qualitatively correspond to the
ionic character of the latter.
5.4.7 One-Electron States in High-Tc Superconductors

Since the discovery of high-temperature superconductivity a large number of
numerical calculations have been made to establish the electron structure of
these remarkable materials. Different band theory methods have been used; the
literature contains detailed analyses. The electronic band structure in super-
conductors is very complex and composed of many energy bands. This is easy
to understand since the unit cells of superconducting crystals contain many
atoms. Here we restrict ourselves to giving the symmetry-allowed contributions
of different atomic (or atom-like) states to crystalline states of different symme-
try in the complex energy bands near the Fermi level.
High-Temperature Superconductors with Space Symmetry Group Di~. The
phenomenon of high-temperature superconductivity was first observed in
cuprates of lanthanum [5.15]. These materials are derived from the oxide
La 2Cu0 4, which has the Di~ space group symmetry (Fig. 5.13). Superconduc-
tivity is demonstrated up to 40 K by the slightly modified compound,
La2-xMxCU04-y, where M is Ba, Sr, or Ca (x '" 0.15) with an oxygen deficiency
of y '" 0.05. A typical picture of the energy bands in a La 2CuO 4 crystal is shown
in Fig. 5.14 [5.16]. In the vicinity of the Fermi level there is a complex 17-branch
energy band with small dispersion along the tetragonal axis Z (r - M direction).
This band is mainly generated by atomic 3d states of Cu and 2p states of oxygen
(17 x 2 states per unit cell). Lanthanum atom 5d, 68 states are coupled to the
conduction band of the crystal and keep the charge state + 3.
Fig. 5.13. Structure of the La 2 Cu0 4 crystal (G = Dl~)
The symmetry of all the band states in the points of high symmetry of the

Brillouin zone is given in Table 5.2. This table lists the symmetry of atomic-like
functions of Cu 3d- and 2p-type, classified according to the irreps of atomic
site symmetry groups and the symmetry of crystal states induced from them.
This table is derived from Table 4.20 of simple induced reps of the space group
D!Z. The atoms Cu and 0(1) occupy the Wyckoff positions a and c belonging to
the set Q (Sect. 4.2.3). Therefore the rows of Table 5.2 related to the Wyckoff
positions a and c are the same as the corresponding rows of Table 4.20. Atoms
0(2) are at the position e . Q. The reps of the space group D!Z induced from the
irreps of the site group Ge = C 4v of the position e may be written as a sum of
simple induced reps for the point a (or b) with Ga (G b ) = D4h :::l G = C 4v (Sect.
4.2.3): e(a 1 ) = a(a 1g + a2 J; e(e) = a(eg + eJ.
Among the atomic states in question the strongest interaction is expected to
be between d Ly2 Cu and Px, Py 0(1) atomic orbitals. Crystal orbitals of the
X
same symmetry induced by them have to belong to quite different energies (due
to repulsion of levels of the same symmetry). This is exactly what is observed
in Fig. 5.14 for the states of symmetry xi. These states determine the total
width of the complex band in question.
Other systems demonstrating high-temperature superconductivity are the
so-called TI-Ba and Bi-Sr cuprates, with T., exceeding 100 K. The actual struc-
ture of these materials is a superlattice of orthorhombic subunits. But the basic
subunit is essentially of tetragonal symmetry. These superconductors seem
to be derived from compounds such as T1 2 Ba 2 Can - 1 Cun 0 2n +4 and
Bi 2 Sr 2 Can - 1 CUn 0 2n + 4 (n = 1,2,3,4; Fig. 5.15) with the symmetry of the space
group D!Z. Full information about the symmetry of crystal states generated by
S-, p-, and d-like functions of atoms Ba(Sr), TI(Bi), Cu and S-, p-like functions of
oxygen atoms is also given in Table 5.2.
Table 5.2. Symmetry of electronic states of crystals of space group Dl1 (I4/mmm)
La 2 Cu04 TI 2 (Bi 2 )Ba 2(Sr 2)Ca._, Cu.0 2.+4 D'7
4h r M X P N
n=1 11 = 2 n=3 n=4 V>

~
Cu - CuI - la a,g(s;z2) 1+ 1+ 1+ I 1+ t;'

Cu 0-
(000) b,g(x2 _ y2) 2+ 2+ 2+ 2 1+ g
4/mmm b29 (xy) 4+ 4+ 1+ 3 2+ 0-
5+ 5+ 3+,4+ 1+,2+ ~
eg(xz, yz) 5
"
~
- - Ca - Cal Ib a,g(s) 1+ 1+ 1+ 3 2- 1'i
:;
(1 1 0) :
4/mmm o
:;
01 - 01 - 2c 1+,2+ 1+,2+ r,4- 1+,r

'"0>
01 ag(s) 5 :;
0-
(1 0 1) b3 .(x) 5- 5- 1+,2+ 3,4 2+,2-
mmm b2.(y) 5- 5- 1+,2+ 1,2 1+,1- g
blu(z) r,4- r,4- 3+,4+ 5 I+,r
~
o
1+,3-
...
'<
02 Ba(Sr) Ba(Sr) Ca Ca2 2e a,(s;z;z2) 1+, r I+,r I, 3 1+,r
o
....,
La TI(Bi) TI(Bi) Ba(Sr) Ba(Sr) (z z 0) b, (x 2 _ y2) 2+,4- 2+,4- 1-,2+ 2,4 1+,2-
(j
02 Cu TI(Bi) TI(Bi) 4mm b2(xy) r,4+ r,4+ I+, r 1,3 1-,2+ go
03 02 Cu2 Cui e(x, y; xz, yz) 5+,5- 5+,5- 3+,3-,4+,4- 5, 5 1+,1-,2+,2-
03 03 Cu2 i
04 03 !:Ii
o
04 ~
:;
0<0
01 02 01 4g a,(s;z) 1+,2+,r,4- 1+,2+,3-,4- 3+,3-,4+,4- 5,5 1+,1+,2-,2- S
02 (z +! z !) b,(x) 5+,5- 5+,5- 1+,1-,2+,2- 1,2,3,4 1+,1-,2+, r (j
5+,5- 5+,5- 1+,1-,2+,2- 1+,1-,2+,2-
...
mm b2(y) 1,2,3,4 ~
-- - -- - - -- ---- S"
::;;
:;
-J
E reV] Fig. 5.14. Electronic energy bands of tetragonal

La 2 Cu0 4 . [5.16]
-4
-6
r F M r x M
Cu
o Ca
OSa
ff~?p
TI
0 0
0 I
, 1'-A5
'01 1'0I
100
I
0
1
o.
10 1 01
6 _ 0
1
I.
6 1-0 1
I'~i'i
,Q 10
o I
, ,I
I I 1
I , 0
6 I 1 I
~I
n=3
Fig. 5.15. Structure of T1 2 Ba 2 Can - 1 CUn 0 2n +4 Fig. 5.16. Structure of the YBa 2 Cu 3 0 7 crystal
crystals (G = DW (G = D~h)
High-Temperature Superconductors with Space Symmetry Group Dl. In

cuprates of yttrium and barium, YBa 2Cu 30 7, high-temperature superconduc-
tivity (7;; ~ 90 K) is a property not only of the basic YBa 2Cu 30 7 structure
(space group G = D~h' Fig. 5.16) but also of the oxygen deficient compounds
YBa2Cu307-~ (0 < b < 0.5). For the basic structure a complex 36-branch band
crossed by the Fermi level is generated by 3d-like atomic states of Cu and
Table 5.3. Symmetry of electronic states of the YBa 2 Cu 3 0 7 crystal (with space symmetry group Dl h )
Atom Dlh r X y Z S T U R
(0 0 0) c!: 0 0) (0 ! 0) (0 0 !) (! ! 0) (0 ! !) (t 0 !) (! t !)
mmm mmm mmm mmm mmm mmm mmm VI
mmm :,..
CuI la ag(s;x 2,y 2,z2) 1+ 1+ 1+ 1+ 1+ 1+ 1+ 1+ 5'
0-
(0 0 0) bJg(xy) 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ c:
mmm b2g (xz) 4+ 4+ 4+ 4+ 4+ 4+ 4+ 4+ 8-
b3g (yz) 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ .g
01 Ie bJ.(z) r r 3+ 3+ 3+ 2- 3+ ~
r g
(0 ! 0) b2.(y) 4- 4- 1+ 4- 1+ 1+ 4- 1+ p;-
mmm b3.(x) r r 2+ r 2+ 2+ r 2+ g.
i:l
1+ 4- 2+
'"
Y Ih ag (S;x 2,y2,Z2) r r 3+ 4+ 1- 'i:l0-"
(! ! !) bJg(xy) 2+ 4- r 1- 1+ 4+ 3+ r
mmm b2g (xz) 4+ r 1- r 3+ 2+ 1+ 4- ~
b3g (yz) 3+ 1- r 4- 4+ 1+ 2+ r ~
o
l+r I+r '<
'"'
04 2q a 1(s;Z;x 2;y2,Z2) I+r I+r l+r l+r l+r I+r o....,
Cu2 (0 0 z) a 2 (xy) 1-2+ 1-2+ 1-2+ 1-2+ 1-2+ 1-2+ r2+ 1-2+
mm b J(x; xz) 3-4+ 3-4+ r4+ 3-4+ r4+ r4+ r4+ r4+ ~
b2(y; yz) 3+4- 3+4- 3+4- 3+4- 3+4- 3+4- 3+4- 3+4-
03 2r adz) 1+2- I+r 3+4- I+r 3+4- 3+4- I+r 3+4-
e.2"
tl:I
o
bJ(x) 3-4+ r4+ 1-2+ r4+ 1-2+ 1-2+ 1-2+ i:l
(tOz) r4+ 0-
mm bz(y) 3+4- 3+4- l+r 3+4- l+r 1+2- 3+4- 1+2- JJ"
5"
02 2s a 1 (z) Pr r4+ I+r 1+2- r4+ 1+2- r4+ 3-4+ n
(0 z) bJ(x) T4+ I+r 3-4+ T4+ I+r r4+ Q
! I+r l+r ~
mm b2(y) 3+4- 1-2+ 3+4- 3+4- 1-2+ 3+4- 1-2+ 1-2+ ~
Ba 2t a J(s) 1+2- r4+ 3+4- I+r 1-2+ 3+4- r4+ 1-2+
(! ! z) .....
0\
mm '"
'-
2p-like states of oxygen [5.17]. The atomic orbitals of Y and Ba practically do

not contribute to the states of this band. The symmetry of band states at symme-
try points of the Brillouin zone generated by atomic orbitals of Cu and
given in Table 5.3. The latter is derived from Table 4.23, taking into account
is
that the irreps of the site symmetry group of the Wyckoff positions q, sand r
induce the composite induced reps
q(ad = a(ag + blJ , s(a 1) = b(ag + b Iu )
q(a 2) = a(au + bIg) , s(a 2) = b(au + bIg)
q(bd = a(b 2g + b3J , s(bd = b(b 2g + b 3u )

q(b 2) = a(b 2u + b 3g ) , s(b 2) = b(b 2u + b3g )
r(a1)=e(bg+bIJ, r(b 1) = e(b2g + b3J
r(a 2) = e(bu + bIg) , r(b 2) = e(b 2u + b3g )
High-Temperature Superconducting Compounds TlBa 1 Ca._ICu.Ol.+3 with
Space Symmetry Group Dl". Figure 5.17 shows the structure of these D!h spe-
cies; the symmetries are listed in Table 5.4 which is derived from Table 4.18.
Table 5.4 gives the symmetry of one-electron states at high symmetry points of
the Brillouin zone in YBa 2 Cu 3 0 6 and TlBa 2 Can _ 1 02n+3 crystals generated by
valence atomic orbitals .
Cu
o Ca
O Sa 1--Q-7
eTi QIA._--,O\
IC?'J 1
0 J I I I
P,------)f
II /.
1010 0.101I
q I
I l'
Uo
I
ct-t--~ I
I 0
:0' 0 1
I
<): 6;
: OJ : <) '6
<) ;06: 10
,I
16 6: -0:
I
I I
101
6:
16
6: 6:~ ;6 I
I I I
I I ,I
A~I
Y II
I I
I
Y
1

I
I
0
I
I I I I
trf-jJ}.rj
I
I --L-9
1/ I /
ti-- - __0' ~ Fig. 5.17. Structure of TIBa 2 Can - 1 CU n 0 2n + 3
n=2 n=3 crystals (G = D!h)
Table 5.4. The symmetry of electronic states in crystals with space symmetry group Dlh (P4/mmm)
YBa 2Cu 30 6 TlBa2Can-ICun02n+3 Dlh r M Z A X R
(0 0 0) H 1 0) (001) (111) (0 1 0) (0 1 1)
n=2 n=3 n=4 4/mmm 4/mmm 4/mmm 4/mmm mmm mmm v.
~
CuI Ca - Cal la a I9 (s; Z2) 1+ 1+ 1+ 1+ 1+ 1+ ...:s

0-
(0 0 0) b,g(x2 _ y2) 2+ 2+ 2+ 2+ 1+ 1+ c
4/mmm b29 (xy) 4+ 4+ 4+ 4+ 2+ 2+ 8.
5+ 5+ 5+ 5+ 3+4+ 3+4+ ~
eg(xz,yz) <>
- 03 04 04 Ib a 19(5) 1+ 1+ r r 1+ r
'"@III
1+ 1+ 2- 1+ :s
(001) a 2u (z) r r g
4/mmm euC".y) 5- 5- 5+ 5+ r4- 3+4+ o
:s
- - Cui - Ie a I9 (s; Z2) 1+ 4+ 1+ 4+ 4- 4- '"
~
:s
0-
(1 1 0) b19(X2 _ y2) 2+ 3+ 2+ 3+ 4- 4-
4+ 1+ 4+ 1+ S-
<>
4/mmm b2g (xy) r r ....,
eg(xz. yz) 5+ 5+ 5+ 5+ I-r l-r ::r
<>
o
Y Tl Tl Tl Id a I9 (s; Z2) 1+ 4+ r 2- 4- 3+ Q
b19(X2 _ y2) 2+ 3+ 4- 1- 4- 3+ 8.,
(1 1 1) (j
4/mmm b2g (xy) 4+ 1+ r r r 4+ ::r
<>
eg(xz,yz) 5+ 5+ 5- 5- 1-2- 1+2+ 3(s.
a 2u (z) r r 1+ 4+ 3+ 4- e:..
eu(x,y) 5- 5- 5+ 5+ 1+2+ 1-2- Ct:I
o
:s
0-
- - 01 - 2/ a 1 s)
i 1+2+ 5- 1+2+ 5- 1+4- 1+4- S
Otl
(0 1 0) b3u (x) 5- 3+4+ 5- 3+4+ 2+4- 2+4- S
mmm b2u (Y) 5- 1+2+ 5- 1+2+ l+r I+r (j
....
btu(z) r4- 5+ 3-4- 5+ r3+ r3+ '<
'"
E
'"
.....
-
Table 5.4 (continued) -..J
-""
04 Ba Ba Ba 2g a l (s; z; Z2) 1+3- l+r l+r l+r 1+2- l+r
Cu2 Ca Ca2 (0 0 z) bl(X2 _ y2) 2+4- 2+4- 2+4- 2+4- l+r 1+2-
!J'
4mm b2(xy) 2-4+ r4+ r4+ r4+ 1-2+ 1-2+ )-
e(x, y; xz, yz) 5+5- 5+5- 5+5- 5+5- 3+3-4+4- 3+r4+4- :g
Ba Cu Cu2 CuI 2h a l (s; z; z2) l+r r4+ l+r r4+ 3+4- 3+4- [
bl (x2 _ y2) 2+4- 1-3+ 2+4- 1-3+ 3+4- 3+4-
o
::;
02 03 Cu2 (t t z)
03 4mm b2(xy) r4+ l+r r4+ 1+3- r4+ 3-4+ o
-.
e(x, y; xz, yz) 5+5- 5+5- 5+5- 5+5- 1+1-2+r 1+1-2+2- 8:
@
02 01 02 01 4i al(s;z) 1+2+r4- 5+5- 1+2+3-4- 5+5- l+r3+4- l+r3+4- p..
03 02 (0 t z) bl(x) 5+5- l-r3+4+ 5+5- 1-2-3+4+ 1-2+3+4- 1-2+3+4- :;.:I
mm b2(y) 5+5- 1+2+r4- 5+5- 1+2+3-4- l+rr4+ l+r3-4+ "

~jIi
s.
!:;.
o
::;
rIO
5.5 Energy Bands and Localized States 173
5.5 Energy Bands and Localized States
5.5.1 Localized Orbitals and Parameters of an Energy Band

The localized orbitals in the case of a degenerate band are connected by a simple
relation (4.2.10) with functions t/lij(k, r) which are not solutions q>!~)(k, r) of the
one-electron equation (5.1.20). The functions t/lij(k, r) are linear combinations of
the solutions q>!~l(k, r) belonging to different energy levels with the same k of a
degenerate band:
t/lij(k,r) = L Uysll.ij(k)q>!~)(k,r) (5.5.1)

YSIl
(5.5.2)
The functions q>!~)(k, r) and the corresponding energy eigenvalues are the solu-
tions of the matrix equation
H(k)U = Ue(k) (5.5.3)
where H(k) is a p x p matrix in the t/liik,r) basis
Hi'j'ij(k) = f t/I~j'(k, r)iltjJij(k, r) dr . (5.5.4)
It is clear that
(5.5.5)
The localized orbitals W;j(r - all) satisfy the system of equations. The latter is
obtained by acting with the operator ii on both sides (4.2.9 or 10) and then
using (5.5.5) and (4.2.8):
iiW;j(r - all) = L
i'j'.'
Ii'j'ij(n' - n) W;'j'(r - all') , (5.5.6)
the quantities Ii'j'ij(n) being
(5.5.7)
Multiplying both sides of (5.5.6) by W;~,(r - a.,), integrating over the direct
space and using the orthogonality of the localized functions we express the
quantities Ii'j'ij(n) through the matrix elements of the operator ii in the basis of
localized functions:
(5.5.8)
or
(5.5.9)
Equation (5.5.7) shows that the integrals (5.5.9) are the coefficients of the Fourier
series for the matrix H(k) periodically depending on k (with the periods B 1 , B z ,
B3 of the reciprocal lattice)
H(k) = L len) exp(ik all) , (5.5.10)

"
where len) is a p x p matrix with the elements given in (5.5.9).
If only one localized function W(r - a) is known, the others may be deter-
mined by applying the operators {j (g E G, the symmetry group of Ii). Then the
matrices len) (5.5.9) and H(k) (5.5.10) may be calculated. Finally the energies e(k)
and the corresponding wave functions are determined according to (5.5.3) and
(5.5.2). Therefore a localized function contains all the information about the
energy band to which it corresponds.
5.5.2 Generation of Localized Functions in Crystals

The symmetry analysis of localized orbitals is only the first step to actually
generating them. We will now consider, in brief, further steps in generating
localized orbitals in practice. For simplicity the states of some energy band are
assumed to form a basis of a simple induced rep.
The procedure of generation involves integration over the Brillouin zone
(4.2.9). In an approximate calculation the integral may be replaced by a sum
over a set of special points k in the Brillouin zone [5.8]:
~1)(r - all) = (IlL) L exp( -ik t a.)t{lW (k t , r) . (5.5.11)

t
The set of special points k t is determined as follows [5.8]. Let
(5.5.12)
be the basis vectors of a new lattice composed of enlarged unit cells, with a i
being the primitive translation vectors of the initial lattice and lij the integral
matrix element of a matrix I with det I = L. The volume of the large unit cell is
L times the volume of the initial unit cell. The primitive vectors of the new
reciprocal lattice are
hj = Li W )jiBi
1 . (5.5.13)
The set K of special points consists of L points in the initial Brillouin

zone
(5.5.14)
qtj are integers. The following relation holds for the points of the set K:
S(a",) = L exp(ik
t
t a",) = L L c5"m Am'
",'
(5.5.15)
We insert in (5.5.11) expression (4.2.8) for 1/J~1)(k, r) through exact localized

functions W;t)(r - a.) and use (5.5.15):
a;Yl)(r - a.) = L W;t)(r - a. - A",) . (5.5.16)

'"
Thus the functions a;t)(r) are the superposition of exact localized functions
W;t)(r - Am) centered on the points separated by the primitive vectors Am of
the new lattice composed of large unit cells, If the transformation 1of (5.5.12) is
such that the overlapping of the functions W;t)(r - A",) centered on the
neighboring sites of a new lattice is negligible, the function a;t) seems to practi-
cally coincide with W;}P) in the region oflocalization of the latter. The dimension
of this region may be established by comparing the results of summation (5.5.11)
over sets K with increasing values of L.
5.5.3 Interpolation Scheme Using Localized Functions

If the symmetry properties of the localized functions of an energy band are
known, it is easy to establish the relations between the elements of the matrix I
(5.5.9) caused by symmetry, to find the independent ones and to express through
them all the rest. Because the functions W;j are localized, the values (5.5.9) de-
crease with increasing lalll --> 00, Keeping a reasonable number of terms in
(5.5.10), we obtain the matrix H(k) as a function of several parameters, which are
not determined by symmetry alone. For any values of these parameters the
eigenvalues a(k) of the matrix H(k) have at any k in the Brillouin zone the same
degree of degeneracy as the energy band considered.
If band energies are known for some points k in the Brillouin zone then they
may be used to find the band parameters mentioned above, Then energy levels
of the band at any point k may be calculated as eigenvalues of the p-order
matrix H (5.5.3), p being the number of energy sheets in the band,
The interpolation scheme using localized functions has in some cases an
advantage over the usually used interpolation scheme of Slater-Koster based on
the atomic function basis [5,18], In particular, in the basis oflocalized functions
energy bands corresponding to different induced reps may be interpolated sepa-
rately.
Consider as an example bands in crystals with symmetry which are oZ
related to localized functions of symmetry a 1g and a2u (the point group D 3d )
centered on Wyckoff positions c, This is the case of two valence bands c(a 1g ),
c(a 2u ) in cubic Si0 2 crystal, of upper valence c(a 1g ) and lowest conduction c(a 2u )
bands in diamond-type crystals (C, Ge, Si). The localized functions of such a
symmetry may be modeled by atomic functions of s- and p-type (four functions
per unit cell):
Wj = (lIv3)(lfJpx +IfJPy +lfJp)<r-T j l2)
Wi = (lIv3)( -lfJpx -lfJpy +lfJp)(r-Tzl2)

(5.5.17)
Wi = (lIv3)(lfJpx -lfJpy -lfJp)(r- T312 ) ;
Wi = (lIv3)( - IfJpx + IfJPy - IfJp)<r- T4 12 )
where
Tl = a(I/4, 1/4, 1/4) , T2 = a( -1/4, -1/4,1/4) ,
T3 = a(I/4, -1/4, -1/4) , T4 = a( -1/4,1/4, -1/4) ;

a is the edge of the elementary cube. The rotation axes are assumed to pass
through the origin of the coordinate system. Then the elements of the group 1d
are contained in G = O~ and may be accompanied by lattice translations. The
other elements of the group G = O~ are the products of the elements from 1d
and inversion accompanied by the improper translation IX = T 1 and lattice
translations. Under operations of the group 1d the functions W; transform
through one another:
gll'j = L Gj;(g) j , (5.5.18)

j
The values Gj;(g) form a matrix of a reducible rep of 1d (the sum of irreps a 1 and
td. They are easy to calculate with the help of (5.5.17).
We can derive from the functions (5.5.17) the quasi-Bloch functions
"'r(k,r) = L exp[ik (a. + d;)] W;(r - a.) , (5.5.19)

where d; = T;/2. According to (5.5.18) the functions "'r(k, r) have the following
transformation properties:
g'" ;(k, r) = L Gj;(g) "'l (gk, r) , (5.5.20)

j
{IgllX} "'r(k,r) = exp(iklX) L Gj;(g)",/(gk,r)

j
. (5.5.21)
The functions (5.5.19) span the space of a rep (reducible) of the little group
G" for any k in the Brillouin zone. At any k there exists a transformation S(k)
diagonalizing the matrix H(k). This transformation means the transition to a
new basis of true Bloch functions. Therefore the quasi-Bloch functions are "'r
the linear combinations of true solutions cp(r) of (5.1.20) belonging to different
eigenvalues for any wave vector k. The action of the operator Ii on such a
function also gives the linear combination of these functions [see (5.5.5)]. Any
linear combination of the functions "'; of a band is orthogonal to any linear
combination of the functions of any other composite (or simple) band. Hence all
the elements of the nondiagonal blocks of the Hamiltonian calculated between
the states of different complex nonintersecting bands are equal to zero. Using
(5.5.20,21) we get
H(k) = G-1(g)H(gk)G(g)
(5.5.22)
H(k) = G-1(g)H(Igk)G(g)
for the band c(a 19 ) as well as for the band c(a2u). It follows from (5.5.19) that the
matrix element Hiik) is a product of periodic functions (with periods of the
reciprocal lattice) and exp[ik (di - ~)]. For the construction of the matrix H(k)
we use the basis consisting of the products of the matrices A!}m) = JilJjm and the
functions f(k) = exp[ik (a. + d i - d)]. The operators {j (g E G) in these spaces
are determined as
(5.5.23)
According to (5.5.22) the matrix H(k) may be expressed as the sum, with arbi-
trary coefficients PI" of linear combinations of basis vectors transforming
according to the unit irrep of 0h. The additional restrictions on coefficients are
due to the symmetry of time reversal and hermiticity of the matrix H(k):
(5.5.24)
The matrix H(k) satisfying all these conditions has the following form [k =
(2n/a) x]:
H 11 (x) = Pl + P4[cos(n(xx + Xy)) + cos(n(xy + x z ))

+ cos(n(x z + xJ)] + Ps[cos(n(xx - Xy))
+ cos(n(xy - x z )) + cos(n(x z - xx))] + P8[cos(2nxJ

+ cos(2nxy) + cos(2nx z )] + ...
H dx) = P2 cos o (xx + Xy)) + P3 [cos (~(Xx - Xy - 2X z ))
+ cos(~(Xx - Xy + 2X z )) ] + P6[COS(~(3Xx - Xy))

(5.5.25)
+ cos(~( -xx + 3Xy)) ]
+ P7 [cos (~(xx + 3xy + 2X z ))

+ COS(~(3Xx + Xy + 2Xz)) + cos(~(Xx + 3xy - 2Xz ))
+ cos (~(3Xx + Xy - 2X z )) ] + ... ,
(5.5.26)
All the coefficients f3i are real. The matrix H (5.5.25, 26) for any values of coeffi-
cients f3i ensures the right degeneracies at the symmetry points and along sym-
metry directions in the Brillouin zone for the energy bands under consideration.
The coefficients f3i may be determined, for example, from the energies at
symmetry points r, X, L [seven values denoted by E(rt), E(rn, E(X 1), E(X 3),
E(Li), E(L1J, E(L"3), for the band c(a 19 )]:
f31 = l2[3E(rn + E(rt)] + l6[E(Xd + E(X3)]

+ t[E(Li) + 2E(L"3) + E(L z )] ;
f32 = l6[E(r1+) - E(r/)] + t[E(Xd - E(X3)]
+ i-[E(L z ) - E(L"3)] ;
f33 + (2f37) = l6[E(rt) - E(rnJ - t[E(Xd - E(X3)] ;
f34 = A[E(rt) + 3E(rnJ - l6[E(X 1) + E(X 3)J

-i4[3E(Ln-2E(L3)-E(Li)] ; (5.5.27)
f35 = l2[E(rt) + 3E(r5+)] -l6[E(Xd + E(X3)]

+ i4[3E(Ln-2E(L3)-E(Li)] ;
f36 = A[E(rt) - E(rnJ + l6[E(X 1) - E(X3)]
+ l2[E(L"3) - E(L z )] ;
5.6 Localized Orbitals in Molecular Models of Crystals 179
P7 = 916 [E(rt) + 3E(rn] + /6 [E(Xd - E(X3)]
- l4[E(Li) + 2E(L"3) + E(L z)] .

For the coefficients Pi of the band c(a2u), analogous expressions are valid
with the substitutions r 1+ -+ r 2-, rs+ -+ r 4-, X 3 -+ X 4' L"3 -+ Lj.
The valence bands c(a 1g ) and c(a 2u ) in the cubic Si0 2 crystal are described
well by this interpolation scheme: only two coefficients Pi are sufficient. Their
values (in eV) are
c(a 19 ): P1 = -26.72, P2 = -0.46, Pi < 0.01, i = 3, ... ,8
c(a 2u ): P1 = -13.88, P2 = -1.20, Pi < 0.02, i = 3, ... ,8
Thus a complex band may be related to a matrix of order equal to the number
of energy sheets in the band. This matrix Hamiltonian is exact, which means
that there exists a set of coefficients Pi such that all the energies in the band are
reproduced correctly.
5.6 Localized Orbitals in Molecular Models of Crystals
5.6.1 Cluster Model of Perfect Crystals

In addition to the models of infinite and cyclic systems the electron structure of
crystals is often described by various cluster models. One tries to obtain the
main features of the electronic energy structure and electron density distribu-
tion by proceeding from a relatively small fragment of the crystal (a molecular
cluster).
The basic difficulty of this approach is the fact that there are many atoms
on and near the surface of the cluster. These atoms do not have regular crystal-
line surroundings and hence distort the electron and energy structure. To mini-
mize the influence of surface atoms it is necessary to complicate the model, that
is, to add additional atoms on the surface and additional electrons on the cluster
as a whole, etc. [5.19]. There are some difficulties in finding a direct correlation
between energy levels and states of the cluster and the modeled perfect crystal.
The symmetry of a cluster is described by a point group Gc coinciding with
the crystal class F of the modeled crystal or with some of its subgroups. One-
electron energy levels and states of a molecular cluster (of a crystal) are classi-
fied according to the irreps of Gc (space group G). Because of different
classification schemes for clusters and crystals symmetry considerations alone
do not permit one to determine the correspondence between energy levels and
states in the two systems. The use of a common symmetry group Gc does not
solve the problem: the restriction of irreps of G to elements of Gc may contain
(e.g., for an irrep with a star of general type) all the irreps of Gc
In the set of a large number of states with equal or nearly equal energies it
is practically impossible to construct linear combinations of Bloch type, espe-

cially in the case of a small cluster in which the translational symmetry of the
crystal is not yet clearly manifested.
5.6.2 Cluster and Crystal Localized Orbitals

The main argument in favor of a molecular cluster model is the following. The
most significant interactions determining the electronic structure of a crystal are
those of an atom with its nearest surroundings. Therefore, a small fragment of
the crystal where these interactions are taken into account should reproduce the
principal features of the electron structure of the entire crystal. Usually the
atomic functions are used as a basis set, that is, the deformation of atomic states
in transforming from separate atoms to a crystal lattice is not taken into ac-
count. Localized orbitals may be considered as deformed atomic orbitals when
the atoms occupy the actual positions in a crystal. This deformation describes
the change in the electron density in a crystal with respect to the sum of the
electron densities of noninteracting atoms (or ions). It seems to be a more ap-
propriate approach where the localized molecular cluster orbitals are compared
with the crystalline ones. This comparison should be done for every valence
band separated from others by intervals of forbidden energies at every k in the
Brillouin zone. The most important problem in cluster modeling of the crystal
is to reproduce correctly the states of upper valence bands, because they are
responsible for chemical bonding in crystals. Later, an energy band
corresponding to some induced rep (i.e., to localized functions of definite sym-
metry) is assumed to be fixed.
The transition from canonical orbitals to localized ones may, in principle,
be realized in a cluster as well as in a crystal. The translational symmetry of
crystalline localized orbitals does not arise, strictly speaking, for cluster local-
ized orbitals, especially for clusters of small size. When the cluster dimensions
are increased the translational symmetry will appear, since in the limit of bulk
crystal the cluster orbitals should transform into crystalline ones. Naturally,
first of all, the orbitals in the center of the cluster, those most distant from the
cluster surface, will take the form of crystalline ones. With increasing cluster
dimensions the region where the cluster orbitals approach crystalline ones will
also increase. It is obvious that in order to have a near-crystalline orbital in the
center of the cluster, the cluster size must not be less than the dimension of the
region where the crystalline orbital is localized.
If the cluster is chosen so that its center coincides with the symmetry centers
of crystalline orbitals with site group Gil its symmetry group Gc will coincide
with Gil' The central cluster orbital will formally have the symmetry of the
corresponding crystal one. The other cluster orbitals will not have this symme-
try even for a cluster oflarge dimensions (when the cluster orbitals approach the
form of crystalline ones) because the other cluster orbitals have the site group
Gc ' c Gil (if Gil # es ' en or env ). Thus, in the framework of the cluster model it is
possible to construct a localized orbital which is close to a crystalline one. As we
have seen (Sect. 5.5.1) the localized orbital determines the structure of the
corresponding crystal energy band and the Bloch states of this band. The
corresponding values in cluster calculations may be taken as the values of the
integrals (5.5.9).
We have considered the case when the valence states of a crystal form one
or several bands which correspond to the localized orbitals centered at one
point as, for example, in diamond-type crystals or in cubic Si0 2 (Sect. 5.4.4). A
more complicated case occurs in crystals where the states of the valence band
are induced from irreps of different site symmetry groups. Examples of such
crystals are fluorite or silver halides (Sect. 5.4.5). To obtain the localized orbitals
for all the valence bands in cluster calculations, it is necessary to take a cluster
of sufficiently large size, as the localization region of crystalline orbitals of two
or more centers should be embedded.
5.6.3 Energy Bands of AgBr from Cluster Calculations of [Ag 14 B 13 r

In this sect on we consider the application of the general procedure described
above to one particular case. We use the results of the electronic structure
calculation of the cluster [Ag14B13]+ to obtain one-electron valence bands in
the AgBr crystal. It is supposed that an atomic valence basis is used. Moreover
the number of basis functions is assumed to be equal to the number of occupied
states in the system, which is an appropriate approach for systems with pure
ionic bonds. Then the space of occupied canonical orbitals is formed by the
given initial space of atomic orbitals. The localized orbitals W(r) may be
identified with the atomic functions of the initial basis. In this basis the first
iteration gives self-consistent solutions of the Hartree-Fock-Roothaan equa-
tions. The cluster calculations determine one-electron energies and the canoni-
cal orbitals of the cluster as a linear combination of atomic functions. The
inverse transformation represents the atomic functions [coinciding with local-
ized functions W(r)] as a linear combination of cluster canonical orbitals. There-
fore the matrix elements of the cluster Hamiltonian calculated with atomic
functions may be expressed through its energy levels.
If the cluster Hamiltonian takes into account the influence of the rest of the
crystal (through a Madelung potential, for example) the matrix elements of the
cluster Hamiltonian calculated with the localized functions of its central part
will be approximately equal to analogous matrix elements of the crystal Hamil-
tonian. The latter determine the energy levels and Bloch states of the bands
under consideration in the modeled crystal. In this way the energy bands of a
crystal are related to the energy levels of a cluster which is the crystal model.
The minimal atomic basis for the electronic structure calculations of the
[Ag14B13]+ cluster contains the atomic functions up to the 4s, 4p orbitals of the
Br atom and 4d of the Ag atom. In the system of energy levels there is a set of
levels which is separated from others by large energy gaps. The corresponding
one-electron states are formed mainly by 4s-functions of Br with a small admix-
ture of 4p-functions of Br and 4d-functions of Ag. For simplicity, only the 4s-
functions of Br in the cluster are assumed to form the space of states belonging
to this set of levels.
The site group GSr of the Br atom in the AgBr crystal coincides with the
symmetry group Gc = Oh of the cluster [Ag 14 Br 13]+' The functions Si
(i = 1,2, ... ,13) span the space of the rep consisting of the following irreps: eg ,
t 1u , t 2g , t 2u and ag (twice). The canonical orbitals of symmetry eg, t 1u , t 2g , t 2u
in the chosen approximation are represented simply by symmetry-adapted com-
binations of s-functions. We write the functions of symmetry a g in the form
1/11 = N(Sl + f3S) ;

(5.6.1)
1/12 = (1 - (2)-1/ 2N[(f3 + Q)Sl - (1 + f3Q)S] ,
where S is a normalized function I}~2 Si, Q is an overlap integral of the

functions Sl (4s-functions of the central Br atom of the cluster) and S,
(5.6.2)
The coefficient f3 depends on the parameters of the cluster Hamiltonian and may
be found only after the electron structure of the cluster is determined.
We denote by E1 and E2 the energy levels belonging to the states (5.6.1). The
application of the procedure described above gives the following expression for
the energy band in AgBr crystal [in the approximation of nearest neighbors and
including only linear terms in the overlap integrals Q = (Sl,S2)]:
E(k) = A + B[cos(akx/2) cos (aky/2) + cos (ak x/2) cos (ak z /2)
+ cos(aky/2) cos(akz/2)] ; (5.6.3)
E1 + f32E2 4j3f32
A = 1 + f32 (1 + f32)2 Q(E 1 - E 2 ) ; (5.6.4)
B - 4(E _ E ){
- 1 2
f3
2j3(l + f32)
+ Q[ f3
j3(1 + f32)
+ f32(f32
(1
-
+ f32)2
1)]}
(5.6.5)
5.6.4 Cyclic Model as a Molecular Model of Crystals

There is another way to ensure that the surroundings of all the atoms of a
cluster mimic actual crystalline conditions. For this it is sufficient to introduce
periodic boundary conditions on opposite sides of a block modeling the main
region of the crystal, i.e., to introduce a cyclic crystal model (Sect. 3.3.2).
When L in (3.3.2) is small the cyclic system can be considered as a special
type of cluster model (cyclic cluster) which, however, does not have the drawbacks
discussed above. The transformation 1(3.3.2) may always be chosen so that the
point symmetry group of the cyclic system coincides with the point group of the
infinite crystal model (symmetrical extension of the unit cell). The cyclic model
also has the translational symmetry defined by the primitive translation vectors
ai (i = 1,2,3). The translation group T(A) of a cyclic model is finite and consists
of L "internal" translations as (8 = 1,2, ... , L) of an extended unit cell. Overall
the cyclic model symmetry group G(A) (in the case of symmetrical extension) is
isomorphous with the factor group G/~ (G is the space group of the infinite
crystal model, TA is the translational subgroup of the superlattice). This simple
relation between the symmetry groups of two crystal models also causes a simple
relation between their irreps [5.20]. From the symmetry point of view the cyclic
system reproduces (in the volume LQ of the cyclic system) the states of an
infinite crystal with wave vectors k (5.5.14) from the set K. Hence there is a strict
symmetry correspondence between the energy levels and states of the two models
even in the case of small cyclic clusters. However, there are some differences in
the results of self-consistent electron structure calculations of infinite crystals
and of the corresponding cyclic systems.
If the potentials in one-electron Hamiltonians of the two models coincide
(in the volume LQ) then the energy levels and one-electron states will be the
same in both models. The self-consistent solutions of Hartree-Fock equations
are different for the two models for two reasons.
First of all, when calculating the electron density in the cyclic model the
sum is taken over the occupied states of a quasi-molecule, i.e., the occupied
states with wave vectors k belonging to the set K. Note that the set (5.5.14) is
one of the possible sets of special points in the Brillouin zone. Therefore the
electron density obtained in the cyclic model coincides with an approximate
expression for the electron density obtained in the infinite crystal model only
when the latter may be approximated with the help of the set of special points
(5.5.14) related to the extended unit cell of the cyclic system.
Secondly, when calculating the potential in the pth iteration in the cyclic
model, only the interactions of atoms within the volume LQ of the cyclic system
are taken into account. This means that the maximum distance between inter-
acting atoms which is taken into account in the cyclic model is equal to half the
linear dimensions of the system.
When the dimensions of the cyclic system are increased the number of states
[and the number of wave vectors k of the Brillouin zone in the sum in (5.5.14)]
taking part in the self-consistent procedure increases. The electron density dis-
tribution in the cyclic system tends to that of the infinite crystal. Similarly, the
potential for the cyclic system tends to that for the infinite crystal.
5.6.5 Localized Orbitals in the Cyclic Model

If the induced rep for a cyclic system has a q-basis then it is possible to form the
localized linear combinations of its canonical functions. The localized function
generation is done in the same way as was described in Sect. 5.5.2. This proce-
dure is approximate for the infinite crystal model because the summation over
the states (the integration over k) is usually done by numerical integration using
the set of special points (Sect. 5.5.2). When applied to a cyclic system this proce-
dure becomes exact, because in this case the summation is really over all states
of the "band" in consideration. The transition to a more exact formula of
numerical integration (summing over larger sets of special points) implies the
transition to cyclic systems oflarger dimensions. The smallest set of special points
assuring the generation of localized functions in the region of their localization
corresponds to the cyclic system of the smallest dimensions reproducing the
crystalline localized orbitals. It is obvious that the dimensions of the localiza-
tion region of the crystalline orbitals determine the cyclic system of minimal size
C reproducing the main features of the crystal electronic structure, since the set
of crystalline localized orbitals corresponding to the occupied one-electron
states (at least in dielectrics and semiconductors) contains all the information
about its electron structure.
Further increase in the size of the cyclic system is unnecessary if the preci-
sion of the energy band parameters obtained is sufficient. One-electron energies
and wave functions of a crystal at the points of the Brillouin zone which are not
contained in the set K (5.5.14) may be calculated by interpolation methods.
6. Induced Representations in the Theory
of Imperfect Crystals
In preceding chapters we have considered so-called perfect crystals. Their sym-

metry is described by Fedorov space groups which have triperiodic translation
groups T as their invariant subgroups. The theory of perfect crystalline solids
explains the bulk properties which do not depend on boundary effects and other
defects of the structure. However, real solids do not demonstrate translational
symmetry. Boundaries and other regions of disruption of translational symme-
try called defects are always present. The defects are classified according to the
dimensions of these regions. When one or a few sites are disturbed, we speak of
point (zero-dimensional) defects. Linear (one-dimensional) defects are called dis-
locations. There are also two-dimensional defects. The surface of a crystal is the
most important two-dimensional defect.
Many practical applications of solids are based on the use of the properties
caused by defects. By varying the defect structure of solids it is possible to
change their physical and chemical properties. All the approaches to a theoreti-
cal description of defect crystals use information about the symmetry of the
system or its model. This and the next section will be devoted to the symmetry
aspects of defects.
First we consider the symmetry of crystals with a single point defect, i.e., the
symmetry of a system where the translation symmetry is completely absent. A
crystal with a single point defect can be seen as a gigantic molecule. In many
cases the electronic states of defects in a crystal are localized in some relatively
small region. The degree of this localization depends on the nature of the defect
and of the host crystal, but the symmetry analysis facilitates the determination
of defect energy levels and states. The application of the site symmetry group
theory is quite useful in such an analysis not only because of the localization of
defect states but also because of the significant influence of the localized charac-
ter of the electron density in the host material. Later we consider the symmetry
of the surface electron states in crystals based on the theory of diperiodic space
groups.
6.1 Point Defects in Crystals
As mentioned point defects have a significant effect on the physical and chemi-
cal properties of crystals and on the mechanisms of solid phase reactions. The

186 6. Induced Representations in the Theory of Imperfect Crystals
defect concentration in a crystal is usually very small. The defects are separated
by large distances and do not affect each other's electron structure. For simplici-
ty, we will let the defects be situated periodically, but make the separation be-
tween defects be very large. The band width of defect states depends primarily
on the degree of overlap of the functions describing the defect electron states
from neighboring cells and decreases rapidly with increasing defect period. For
large defect periods the arrangement of defects is not important so that we can
use a defect distribution which is most convenient for the calculations. The
model of a single defect seems to be one of the most appropriate. The model
of periodic defect is also used for the study of a single defect in crystal but it
describes real structures too.
6.1.1 Single Defect Model

As mentioned above, a single defect embedded in a crystal disrupts the transla-
tional symmetry of a perfect crystal so that it may be considered as a gigantic
molecule with a point symmetry group inherent to molecules. There are two
cases: an atomic point defect, which occupies one point of a crystal lattice or an
interstitial position and can be a substitutional impurity, vacancy or interstitial
atom; and a molecular point defect, which occupies several atomic or inter-
stitial points of a crystal lattice and can be composed of an impurity molecule
or a cluster of several vacancies at neighboring lattice points. In the first case
the symmetry group of the defect crystal is fully determined by the site sym-
metry of the point q where the atomic defect appears. In a crystal with a sym-
morphic space group the atomic defect may occupy the position q with the
symmetry of the crystal class or one of its subgroups. In nonsymmorphic
crystals the point group of the crystal with a single point defect of atomic type
is always a subgroup of the crystal class.
As an example, consider NaCI- and diamond-type crystals (space groups O~
and Oh respectively). In alkali halide crystals with a NaCI structure impurity
centers formed by singly charged Hg-like impurity ions at cation lattice points
(e.g., KCI : TJ+) are well studied. The symmetry of a crystal with such a point
defect is described by the point group Oh' which is the site symmetry group of
the cation coinciding with the point group of the perfect crystal.
Another type of defect common in alkali halide crystals is an electron
captured by an anionic vacancy, called an F-center. It also has the symmetry
group 0h.
An impurity nitrogen atom in diamond crystal can substitute a carbon
atom with site symmetry 1'.J. Then the crystal with such a point defect has lower
point symmetry, 1'.J, than the perfect crystal (diamond belongs to the crystal
class 0h).
In a crystal with point defects of molecular type the center of the impurity
molecule is situated at a point with some site symmetry. A molecular defect has
its own point symmetry so that the point symmetry of the whole system is
determined by the common elements of two groups: the point group of the
6.1 Point Defects in Crystals 187
./ ./ Fig.6.1. F-center aggregates in alkali halide crystals shown
@
by the large circles
Y ........
F3-Center, C3v ,/ ,/
isolated molecule and the site symmetry group of the site where the impurity
molecule is situated_ However, it is necessary to also take into account the
orientation of the impurity molecule with respect to the crystal symmetry axes_
Let us consider some examples of molecular-type defects in alkali halide
crystals_ F-aggregate centers are two or more F-centers at neighboring anionic
lattice points_ The simplest is an M(F2 }-center, which is analogous to a
hydrogen molecule. (Note that such structures do not exist outside of crystals_)
The symmetry of an M -center in alkali halide crystals is described by the
point group D2h (a free hydrogen molecule has symmetry D ooh )- The more com-
plex aggregate of three F-centers [R(F3 }-center] at neighboring lattice points
has the symmetry C3v ' The F-aggregate center from four F-centers has two
configurations: an Nrcenter of symmetry 1d and an N1-center of symmetry C2h
(Fig_ 6_0-
Initially it was assumed that when a point defect appears the configuration
of the crystal matrix around the defect did not change (the model of a rigid
lattice). In reality this assumption is approximately correct only for some point
defects and as a rule only for the ground electron state. Excitation of the defect
electrons causes significant reconstruction of the defect's surroundings so that
the symmetry of the entire system may change. In the first approximation, the
distortion of the crystal lattice by a defect is neglected. Then this distortion is
taken into account with approximate wave functions obtained for the rigid lat-
tice model. Therefore, initially, the symmetry is approximated in the frame of
the rigid lattice model.
However, knowledge of the actual symmetry of a crystal with a point defect
is necessary for correct understanding of all its properties: the symmetry deter-
mines the selection rules for optical transitions in the defect, the symmetry and
the splitting of local energy levels in external fields, the features of EPR and
NMR spectra, etc_
The single defect localized electron states of a given energy level span the
space of an irrep of defect point symmetry group GD - The band states of a perfect
crystal are classified according to irreps of the space group G. It is useful to

determine which band and localized states are allowed to mix (e.g., for calculat-
ing the electron structure from atomic basis functions). We consider the appear-
ance of a point defect as a perturbation of a perfect crystal. According to pertur-
bation theory, only states with the same symmetry may interact with one
another. The common symmetry group of both systems is Go c G. Let Pbe an
irrep of Go which describes one of the defect states. To establish the possibility
of its mixing with the perfect crystal states of symmetry D(*"Y) it is sufficient to
know whether the restriction D(*"Y) lGo contains the irrep p (Sect. 4.5.1). If the
state of symmetry D(*"OY) does not contain the state of symmetry p, then the
contribution of the states with k near ko is small according to the k - p pertur-
bation theory (Sect. 5.3.3), although it is not equal to zero due to the symmetry.
As an example, let us consider the s-states of an impurity at a cation site
(Wyckoff position a, site group D2h , s-state has symmetry ag ) or at an anion site
(Wyckoff position f, site group C 2v , s-state has symmetry a 1 ) in rutile Ti0 2
From band calculations we know the symmetry of states on the boundaries of
the forbidden gap in a rutile Ti0 2 crystal: r/ (the bottom of the lowest conduc-
tion band) and r3+ (the top of the upper valence band). From Table 4.5 we find

d Irect I
y. 1r+ 2h = ag ;
1 ..ID(a) r+
3..ID(a)
2h =
. t h e s-states 0 f
b19' I.e., an may mIX
Impunty .
with the states of the bottom of the lowest conduction band, but not with the
states of the top of the uppermost valence band. The anion site is at the Wyckoff
position f (Gf = C2v ). Following the prescriptions of 2b in Sect. 4.5.1 we get
r 1+ lCY.? = a 1; r3+ lCy';> = b2, i.e., the s-states of an impurity at an anion site
may mix with the states of the bottom of the lowest conduction band but not
with the states of the top of the uppermost valence band.
6.1.2 Cluster Model of Imperfect Crystals

To understand the nature of a point defect in a crystal and the degree of its
influence on the properties of the crystal matrix it is necessary to relate the local
energy levels of the defect to the energy band structure of the perfect crystal.
But these two systems (crystal with defect and perfect crystal) have different
symmetries and the classification of electron states is made according to irreps
of either a point group (for a crystal with a defect) or a space group (for a perfect
crystal).
Two approaches were proposed: a molecular cluster approach and a cyclic
system approach. In the molecular cluster approximation it is rather easy to
establish the relationship between energy levels and one-electron states of a
molecular cluster with and without a point defect. The symmetries of both
systems are described either by the same point group or by a point group which
is a subgroup of the other (in the case of a molecular-type defect). Hence, in the
cluster model the relationship between the classification schemes of electron
energy levels and states of perfect and imperfect crystals is simple. But the rela-
tionship between the cluster electron energy structure and that of a perfect
crystal is much more complicated. One possible way of establishing this rela-
6.1 Point Defects in Crystals 189
tionship (via the localized functions of the systems) was discussed in

Sect. 5.6.2.
6.1.3 Cyclic Model of Imperfect Crystals

The cyclic system symmetry group G(A) was defined in Sect. 3.3.2. It contains a
finite group T(A) of internal translations. Placing a point defect inside the vol-
ume of a cyclic system disturbs its translational symmetry. The symmetry group
of a cyclic system with a single defect is a point group Gt) coinciding with the
point group of the cyclic model without defects or is its subgroup (if the defect
is of molecular type) as in the case of the cluster model. But in the cyclic model
the solutions must satisfy cyclic boundary conditions. Realization of a cyclic
model description of an imperfect crystal implies calculating the electron struc-
ture of a system with a large but finite number of atoms. It is necessary to
make these calculations twice (as in the cluster model): with and without a
defect in the system. Comparison of the results will clearly reveal the changes
of the electron energy levels and states caused by a single point defect. In the
cyclic model it is easy to relate the energy levels of the cyclic system without
a defect to the band energies of a crystal, as the latter are reproduced (at least
with respect to the symmetry) by the cyclic model in a set of k-points (5.5.14)
in the Brillouin zone (Sect. 5.6.4). Thus the position of point defect energy
levels relative to energy bands of a crystal may be found.
6.1.4 Band Model of Imperfect Crystals

Both models considered in Sects. 6.1.2 and 6.1.3 describe a single defect in a
crystal. Another approach is to assume that the defects are situated periodically
in the lattice of the host crystal. This system may also be regarded as a perfect
crystal with a new translational and point symmetry imposed by the geometry
of the defect arrangement. The choice of the translational symmetry of such
a system has to correspond to its point symmetry. Let us consider the case
when the symmetry of defect in the crystal is the highest site symmetry of a
new structure. Then, it determines the crystal class and the point symmetry of
a new Bravais lattice. This condition may be satisfied by different ways.
As an example let us consider an oxygen diatomic molecule substituting
an oxygen ion in the site a of MgO crystal (space group O~) and oriented in
[110] direction. The intersection of the molecular symmetry group OM = Dooh
with the site symmetry group of Wyckoff position aGa = Oh gives the group
Gd = D 2h . Therefore in this case the space group of a crystal with a periodic
defect is of crystal class D2h (orthorhombic system). The translation vectors
Ai (i = 1,2,3) of a new lattice, the augmentation L of a unit cell volume with
respect to the primitive unit cell of a host crystal and Schon flies and interna-
tional symbols of corresponding space group G are the following:
1. AI = (al2)(nt> -nt>O), A2 = (al2)(n2,n2,O), A3 = (al2)(O,0,2n3);
L = 2njn2n3; G = Dih (Pmmm);
2. a) Aj = a(nj,O,O), A2 = a(O,nj,O), A3 = a(O,O,n2);

L = 4nTn2; G = D1~ (Cmmm);
b) Aj = (al2)(nj,nj,2n2), A2 = (al2)( -nj, -nj,2n2),
A3 = (al2)(n3, -n3'O);
L = 4njn2n3; G = D1~ (Cmmm);
c) Aj = (al2)(nj, -nj,2n2), A2 = (al2)( -nj,nj,2n2),
A3 = (al2)(n3,n3'O);
L = 4njn2n3; G= D1~ (Cmmm);
The cases (b) and (c) are geometrically different as the vector A3 is
perpendicular (case b) or parallel (case c) to the molecular defect axis.
3. Aj = (al2)(nj,nj,2n2)' A2 = (al2)(nj, -nj,2n2), A3 = a(nj,O,O);
L = 4nTn2; G = D~1 (Fmmm);
4. Aj = (al2)(nt,nj,O), A2 = (al2)(n2, -n2'O),
A3 = (a/4)(nj +n2,nj-n2,2n3);
L = njn2n3; G = D~1 (Immm),
nj,n2,n3 are all of the same parity.
The crystal with a periodic defect simply has a unit cell which is larger
than that of the host crystal. Hence band theory methods are fully applicable
to these systems. Strictly speaking, defect energy levels form a defect band.
That is why this approach is also called the band model of point defects in a
crystal. If the period of the defects is sufficiently large, this model gives results
correlating with those of the cyclic model of a single point defect. Indeed the
width of the defect band depends first of all on the degree of overlap of the
functions describing the interacting electron states in neighboring cells and
decreases rapidly with increasing defect period. Note that the states with k = 0
in this band model have the same symmetry (inside the volume of the unit cell)
as the functions in the cyclic model of a single point defect.
Applying the band model of a point defect in a crystal is a very time-
consuming procedure because the unit cell of the imperfect crystal usually
contains a large number of atoms. Consider the example of a crystal with dia-
mond structure having two atoms per unit cell and a face-centered cubic lattice
(space group Ol) with lattice constant a. Let atom B substitute one of the atoms
A of the host crystal. In the band model of the point defect A : BA it is appropri-
ate to use symmetrical extensions of the unit cell which preserve the point
symmetry of the host crystal. In our case the following symmetrically extended
unit cells are possible (RD is the distance between defects in neighboring cells):
A 2n'-lB , n = 2, ... , RD = an/.J2 ;
ASn'-lB , n = 1,2, ... , R D = an ; (6.1.1)
A 32n '-lB , n = 1,2, ... , RD = J3an
In the band model it is necessary to find the variation of the defect band width
with the period of the defect. In our example we must calculate this for crystals
6.1 Point Detects in Crystals 191
with unit cells A7B (RD = a), A\5B (RD = V2a), A31B (RD = V3a), A53B
(RD = 3 alV2) , A63B (RD = 2a), and so on.
In practice, such calculations were made in the framework of nonem-
pirical Hartree-Fock description [6.1]. Semi-empirical methods of quantum
chemistry were used, too. For example, extended Huckel calculations in the
band model of a vacancy Vc and a nitrogen atom impurity Nc at the site of
a carbon atom C were made for C63 Vc and C63NC (RD = 2a) at the r and X
points of the Brillouin zone of a simple cubic lattice [6.2]. The difference L1 rx
of the energies at these points estimates the dispersion of the defect band. The
band model for the defect Nc gives L1 rx -O.1 eV, i.e., the C63NC unit cell is
sufficiently large to reproduce the electron structure of the single defect Nc in
diamond crystal. For the vacancy Vc the dispersion is too large (L1rx = 1 eV).
This means that the electron wave functions of neighboring defects (RD = 2a)
overlap considerably. It is necessary to increase the unit cell to get results cor-
responding to a single vacancy model.
6.1.5 Localized Orbitals in the Band Model of Point Defects

Within the band model the energy level of a point defect may be estimated
without significantly increasing the unit cell. Let a defect band be separated
from the bands of the host crystal at any k in the Brillouin zone and let the states
of this band span the space of some induced rep related to the site where the
defect is situated. Then there exist localized functions W(r - Ro) centered on
the defects. The degree of overlap of these functions on neighboring defect sites
determines the width of the defect band. For simplicity, the defect band is
assumed to be nondegenerate. lio is defined as the one-electron Hamiltonian
of the crystal with a periodic defect. Then the energy
(6.1.2)
is the "center of gravity" of the defect band and is approximately the energy of
a single defect.
Let us express the functions W(r - Ro) through Bloch functions I/Io(k, r)
which satisfy the equation
liol/lo(k, r) = Eo(k)l/Io(k, r) , (6.1.3)
f
[V/(21llJ E(k)dk = L -1 L E(k
t
t) , (6.1.4)
Eo = L -1
kk'
L exp(i(k - f
k') Ro) I/I/j(k, r)liol/lo(k', r) dr
(6.1.5)
the wave vector k taking the values in the Brillouin zone corresponding to the
periodic defect model. A "special points" method of numerical calculation of an
integral over the Brillouin zone may be used [6.3]. Thus to estimate Eo for a
single defect it is sufficient to calculate Eo(k) for only several special points in
the Brillouin zone of a crystal with a periodic defect. The energy Eo rapidly
converges to the energy of a single defect when the period of the defect increases.
This rapid convergence may be illustrated with the example of a KCI : H center.
Using the extended Hucke! method for energy calculations of a crystal with unit
cells K4 Cl 3 H and Kg Cl 7 H the values obtained for Eo were - 9.89 eV (the rand
R points in the Brillouin zone of the simple cubic lattice were used as special
points) and -9.86 eV (with special points r, X, L in the Brillouin zone of a
face-centered cubic lattice), respectively.
6.2 Diperiodic Space Groups. Surface Electron States
To model the electronic structure of surface states of crystals three basic

approaches are used: the cluster, slab, and semi-infinite crystal models [6.5].
The latter is the most exact because it takes into account all the atoms of the
crystal with a surface. A semi-infinite crystal is a three-dimensional object. Its
symmetry group contains, in addition to translations in the surface plane, only
the rotations and mirror reflections which keep the atoms in the planes parallel
to the surface. Only 17 such groups exist. Formally these groups are isomor-
phous with diperiodic space groups in two dimensions. They are called plane
groups.
In the molecular cluster approach a crystal with a surface is modeled by a
finite system consisting of the atoms on the surface and of some atomic planes
nearest to it. The diperiodicity of the surface is not taken into account. The
symmetry of such a model is described by one of the crystallographic point
groups.
In the slab model a crystal with a surface is approximated by a slab of finite
thickness. The symmetry group of this model allows the existence of symmetry
operations that move the atoms out of the plane of the layer but bring them into
positions occupied by other atoms of the slab. These are space diperiodic groups
in three dimensions. They are also called the layer groups. We denote them by
DG. These groups also describe the symmetry of thin films. In layered crystals
the interaction between the nearest layers is usually weaker than that between
nearest atoms in the same layer plane. Therefore the slab model is a convenient
approximation for such crystals. Layer groups describe the symmetry of this
model.
6.2.1 Diperiodic (Layer) Space Groups

The diperiodic groups DG are subgroups of the Euclidean group E 3 . The theory
of these groups may be developed in the same way as the theory of triperiodic
6.2 Diperiodic Space Groups. Surface Electron States 193
(Fed oro v) space groups G. A group DG contains a subgroup of two-dimensional

translations T(2) with elements (Ia,,), where
(6.2.1)
is an arbitrary translation vector of the plane lattice, and a 1 and a 2 are unit cell
(primitive) translation vectors. The ends of all vectors a" beginning at some
origin 0 form a two-dimensional Bravais lattice.
The point symmetry group Go of this lattice must satisfy the following re-
quirements, which are supplementary to those mentioned in Sect. 3.3: symmetry
axes of order n (n > 2) must be perpendicular to the plane of vectors aI' a 2 (layer
plane), reflection planes must be either perpendicular or parallel to this plane.
These requirements restrict the number of possible two-dimensional lattices.
There exist only five plane lattices distributed over four crystal systems
("syngonies", see [6.6]): 1) oblique; 2) rectangular; 3) centered rectangular; 4)
square; 5) hexagonal. Screw axes in layer groups may be only the second-order
axes lying in the layer plane. Improper translations in operations of reflection in
glide planes (parallel or perpendicular to the layer plane) must be oriented along
the layer plane.
In all, there exist 80 layer groups DO i(i= 1,2, ... ,80, see Table 6.1)
[6.6]. Two systems of notations are used for layer groups: those of Schonflies
and the international ones. The international symbol contains, first, the infor-
mation about the two-dimensional Bravais lattice type: P (primitive) or C
(centered). Then the information about symmetry elements is given. The screw
axes (of second order) have the subscript 1. The glide reflection planes are
denoted as follows: m, n, a, b, c, d depending on the direction of the improper
translations [6.6]. For example, P 211 and P 112 denote different layer groups.
In the first group the axis of second order is perpendicular to the layer plane,
in the second it lies in the layer plane and is directed along the a2 direction.
Any element of the layer group may be written as (R;I Vi + an), where an and
Vi are lattice and improper translations.
Let a3 be a vector which does not lie in the layer plane. A set of elements
(EI n3a3) forms a group T3 of one-dimensional translations. Consider the
elements
(6.2.2)
The set (6.2.2) of symmetry operations contains a group of three-dimensional

translations (Ia" + n3 a3 ) E T.
The set (6.2.2) is some space group provided the translational symmetry (the
group T) is compatible with the point symmetry F of the layer group DG. This
condition is fulfilled if the vector a 3 is chosen perpendicular to the layer plane.
Indeed the translations (Ia,,) E T(2) c T are compatible with F as they are the
elements of DG. The compatibility of the translations (ln 3 a 3 ) E T3 with point
group F follows from the fact that the rotations (proper and improper) from DG
transform the layer into itself and, therefore, the vector perpendicular to the
Table 6.1. Correspondence between two-dimensional (DG) and Fedorov (G) space groupsa
~
'"
DG G DG G DG G DG G
~
! PI C: I 21 P22 12 1 D32 18 41 Pamm Dih 51 61 P4/mmm D1h 123
5'
2 PI c;' 2 22 C222 D~ 21 42 Pnma Dih 53 62 P4/nbm Dlh 125 0-
c::
J P211 q 3 23 P2mm qv 25 43 Paba D~h 54 63 P4/mbm Dlh 127
4 Pmll C,1 6 24 Pmm2 25 44 Pmba Dih 55 64 P4/nmm Dlh 129 8-
q"
5 Pbll C; 7 25 Pm2 1a Civ 26 45 Pabm D"2h 57 65 P3 el 143 .g
6 P2/mll qh 10 26 Pbm2 1 Civ 26 46 Pnmm D13
2h 59 66 P3 eli 147 ~
7 P2/bll cth 13 27 Pbb2 27 47 Cmmm D19
2h 65 67 P312 D~ 149 "::;
Ci"
8 PI12 q 3 28 P2ma Civ 28 48 Camm D21
2h 67 68 P321 DS 150 ?lo
9 PI12 1 Ci 4 29 Pam2 ctv 28 49 P4 C1 75 69 P3ml elv 156 ::;
10 ClI2 Ci 5 30 Pab2 1 Civ 29 50 P4 81 81 70 P31m qv 157 '"5'
l!. Pllm C,1 6 31 Pnb2 qv 30 51 P4/m Clh 83 71 P312/m D~d 162
C,2 164
~
11. Plla 7 32 Pnm2 1 Civ 31 52 P4/n Clh 85 72 P32/ml D~d
Cllm 8 33 P2ba 32 53 P422 89 73 P6 168
;l
.u C; qv D1 CJ
14 P112/m qh 10 34 C2mm 35 54 P42 12 Dl 90 74 P6 174 "...,o
C"2v elh '<
15 PI12dm Cih 11 35 Cmm2 q~ 38 55 P4mm Clv 99 75 P6/m qh 175 o
....,
16 C112/m Cih 12 36 Cam2 q~ 39 56 P4bm Clv 100 76 P622 DJ 177 3'
17 P112/a Cih 13 37 Pmmm D~h 47 57 P42m D~d III 77 P6mm qv 183 "g
...,
18 P112 1/a Cih 14 38 Pama Dlh 49 58 P42 1m Dld 113 78 P6m2 D~h 187 p.
19 P222 D12 16 39 Pnba Dih 50 59 P4m2 Did 115 79 P62m D~h 189 '"
(j
...,
20 P222 1 Di 17 40 Pmma Dih 51 60 P4b2 Did 117 80 P6/mmm DJh 191 '<
'"E.
a The numbers of 17 plane groups are underlined, '"
layer is transformed into a vector also perpendicular to the layer. Thus the set
of elements (6.2.2) forms one of the three-periodic space groups G. Moreover the
translational group T3 is invariant in G: with the translation (Ela3) it contains
also the translation (EIR;a 3 ) for any R; from (6.2.2). Therefore the group G may
be expressed as a semi-direct product
G = T3 1\ DG (6.2.3)
and be decomposed into co sets with respect to T3
(6.2.4)
For some layer groups of oblique and rectangular crystal systems (DG 1, 2,
8-18) the vector a 3 may be inclined to the layer plane.
We see that every layer group DG is related to one of the Fedorov space
groups G in three dimensions. The groups G have the structure of the semi-
direct product (6.2.3). In the cases when a space group G may be represented as
a semi-direct product (6.2.3) in two different manners it generates two non-
isomorphous layer groups. For example, the layer groups P211 and P112 are
related to one space group P2 (CD with two different settings (the second-order
axis is oriented along the z- and y-directions, respectively). The space group
P2/b (Cih) generates two layer groups P2/b 11 and P 112/a. In the first group the
rotation axis is perpendicular to the layer and the layer plane itself is a glide
plane with an improper translation on a half period along the y-direction. In the
second group the rotation axis is directed along the y-axis; the glide reflection
plane is perpendicular to the layer (and to the rotation axis) and reflection in
this plane is followed by improper translation on the half period along the x-
direction. The latter corresponds to the space group Cih with a nonconventional
setting.
A particular case of layer groups is that of the so-called plane groups
mentioned above. Formally they are the symmetry groups of diperiodic systems
in two dimensions. They correspond to the layer groups which do not contain
the rotation axes lying in the layer plane and the reflection planes coinciding
with the layer plane. Semi-infinite crystals with plane diperiodic surfaces have
plane groups as the groups of symmetry.
6.2.2 Site Symmetry in Layer Groups

The Wigner-Seitz cell for an arbitrary group DG is a right prism with a directrix
lying in the layer plane. The projection of the Wigner-Seitz cell on the layer
plane is a polygon constructed from the basis vectors a 1 and a2. The Wigner-
Seitz cell of the corresponding triperiodic group G is derived by construction of
additional planes perpendicular to the vectors a3 (and perhaps to their integer
combinations with the vectors aj and a2) and passing though their midpoints.
Thus the Wigner-Seitz cell of the group G is a part of that for the corresponding
group DG.
The site symmetry groups for the majority of positions belonging to both
Wigner-Seitz cells (of G and of DG) are identical since they are determined by
the same set of symmetry operations. The only exception may be for the points
on the sides of the group G cell which are absent in that of the group DG. The
existence of translational symmetry in the third dimension in the group G may
give rise to additional symmetry operations in site symmetry groups for these
points in the group G with respect to DG. The part of the Wigner-Seitz cell of
the layer group DG which has no common points with the cell of the corre-
sponding group G contains the points of general position and the points with
site symmetry defined by vertical planes and rotation axes. These types of site
symmetry are already represented in the common part of the cells for G and DG.
Therefore the set of points with different types of site symmetry in the group G
is larger than that in the group DG. Thus the points of different types of site
symmetry (Wyckoff positions) in DG may be specified by the same roman letters
as in the corresponding groups G.
In layer groups the inversion center and the points of intersection of vertical
and horizontal symmetry elements may be situated only in the layer plane. This
means that the symmetry points of the Wigner-Seitz cell for a layer group DG
may appear only in its intersection with the layer plane.
As an example consider the layer group P112da (DG 18). This group is
related to the group G = Cih (P2db) of a monoclinic crystal system with a
nonconventional setting. Figure 6.2a shows the Wigner-Seitz cells for the
groups G = Cih (the primitive translation vectors a\3), a~3), a~3); a~3) ..L a\3), a~3
and DG 18 (the primitive vectors a 1 = a\3) and a2 = a~3. The section of the
Wigner-Seitz cell of the group DG 18 by the layer plane is marked in Fig. 6.2a
by horizontal hatching. The orientations in the space of symmetry elements C2
and (J [the orthogonal parts of the combined operations (C 2 Iv) and (Jlv)] in G
and DG are also shown. The origin is chosen to be at the inversion center. In
this case the group T3 consists of the translations n3a~).
(a) (b)
Fig. 6.2a, b. Space groups G = qh and DG 18: (a) Wigner-Seitz unit cells; (b) Brillouin zones
The points a, b, c, d indicated in Fig. 6.2a are the symmetry points in the
Wigner-Seitz cell of the space group G = Cih' Their site symmetry groups are
Ci . The other points are of general position. In the layer group DG 18 the points
a and c are symmetry points with site group Ci The rest are points of general
position.
6.2.3 Irreducible Representations of Diperiodic Groups

The irreps oflayer groups DG may be generated in the same way as for the space
groups G. But, as we shall see, all the irreps of DG are contained in the irreps of
the related space group G. The simple connection between the irreps of G and
DG may be established using (6.2.3). According to the little group method (Sect.
2.3.4) the little group for the unity irrep of the invariant subgroup H coincides
with the whole group G. The allowed (small) irreps of the little group compose
a part of all the irreps of G. In this case there is a simple relation between the
allowed irreps of the little group and the irreps of the factor group G/H: every
irrep of G/H generates some allowed irrep of G in which all the elements of the
coset giH in the decomposition G = LigiH are mapped by the same matrix,
namely by the matrix of the factor-group G/H irrep for the coset giH.
Let us take T3 as an invariant subgroup of the space group G. Then the
layer group DG is isomorphous to the factor group G/T3 . Therefore every irrep
of DG is related to a definite irrep of G (of the same dimension). In these irreps
of G all the elements of the coset (R;I Vi + a.) T3 are mapped by the same matrix.
In particular, all the translations in T3 (coset (EIO)T3) are mapped by unit
matrices.
We choose in the space of an irrep of G the basis which is at the same time
the basis of the irreps of its invariant subgroup T3 . Then the translations
belonging to T3 are mapped by the diagonal matrices with the elements
exp ( - ik n3 a ~3). These matrices become the unit ones if at any integer n3
exp( -ik(3)'n3a~3) = 1 . (6.2.5)
Condition (6.2.5) holds for any k(3) in the plane II perpendicular to the vector
a~3) and passing through the origin of the coordinate system in the reciprocal
space (k(3) = 0). The plane II contains the primitive vectors B~3) and B~3) of
the reciprocal lattice for the space group O. The third vector B~3) is perpen-
dicular to the layer plane and to the primitive translation vectors a~3) and a~3)
of the direct lattice lying in this plane. The wave vector k(3) in the plane II
may be decomposed over the vectors B~3) and B~3)
k(3) = aj B\3) + a2B~3) (6.2.6)
The primitive vectors B j and B2 of the preciprocallattice for the layer group
DO lie in the layer plane determined by the vectors aj = ap) and a2 = a~3)
[(B(aj) = 2nl5U ' i,j = 1,2]. Any vector k of the two-dimensional Brillouin
zone of the layer group DO has the decomposition
198 6. Induced Representations in the Theory oflmperfect Crystals
(6.2.7)
If the vector a~3) is not perpendicular to the layer plane the vector B~3) or B~3)
(or both) do not lie in this plane and k(3) from (6.2.6) does not lie in the
Brillouin zone of DO. The correspondence between k(3) from (6.2.6) and k
from (6.2.7) is established by the law of transformation of basic vectors of
irreps under translation operations in layer planes. To satisfy this condition it
is necessary that
k(3). a\3) = 2nlY.; = k a; = 2nf3; ,
I.e.,
i = 1,2 . (6.2.8)
It is easy to check that the vectors k are the projections of k(3) onto the layer
plane and that the point groups of wave vectors (6.2.6) and (6.2.7) are identical.
If the vector a~3) is perpendicular to the layer plane the vectors k(3) and k
coincide with one another, i.e., both lie in the Brillouin zone of DG.
The star of any vector (6.2.6) lies entirely in the plane of vectors B?) and
B~3). Therefore the correspondence of irreps mentioned above takes place both
for allowed (small) irreps of (little) wave vector groups Gk(l) (in G) and Gk (in
DG) and for the full irreps of G and DG. So the subduction of any small irrep of
wave vector group Gk(l) with k(3) from (6.2.6) [full irrep of G with wave vector
star from (6.2.6)] on the elements of the layer group DG generates some small
irrep of the little group G" with k from (6.2.7) [full irrep of DG with wave vector
stars from (6.2.7)] of the same dimension.
If DG contains reflections (or glide reflections) in the layer plane, the point
group of the wave vector G" at any k in the Brillouin zone also contains
this element. In such layer groups there is no point of general position in the
Brillouin zone. Note that the Brillouin zone of any space group G has points of
general position.
If the vector a~) is perpendicular to the layer plane the two-dimensional
Brillouin zone (BZ-2) of DG is a section of the three-dimensional Brillouin zone
(BZ-3) of the corresponding space group G. If the latter has the conventional
setting of the crystallographic axes the notations of the point in BZ-2 coincide
with those in the section of BZ-3.
As an example consider the generation of irreps for the layer group DG 18
from the irreps of the space group G = Cih' Figure 6.2b shows: BZ-3 for the
group G = Cih with nonconventional setting of the crystallographic axes; and
BZ-2 (hatched rectangle) for DG 18. The conventional notations for symmetry
points in BZ-3 (in brackets) and BZ-2 are used. The points r, D, B, Z of BZ-3
correspond to the points r, S, X, Y of BZ-2.
According to the theory developed above the restrictions of the small irreps
of the little groups for the wave vectors r, D, B, Z of G = Cih to the elements of
DG 18 are the small irreps of the little groups for the wave vectors r, S, X, Y of
Table 6.2. Characters of small irreducible

representations of the group G = Cih (DG 18) with
k = D(S), B(X), Z(Y)
Cih DG 18 (EIO) (l10) (C 2 Iv) (ulv)
D+I S+I 1 1 i i
D; S+2 1 1 -i -i
D-I S-I 1 -1 i -i
D2 S2 1 -1 -i i
B, X, 2 0 0 0
Z, Y, 2 0 0 0
DG 18. The point group of all these wave vectors is C2h It follows from [6.7] (see
also Table 6.2) that the groups of wave vectors r(S) and X(Y) for DG 18 [gener-
ated by the group of wave vector r(D) and B(Z) for G = Cih] have four one-
dimensional irreps and one two-dimensional irrep respectively (Table 6.2). For
k = 0 (r-point) the irreps of the groups G = Cih and DG 18 coincide with the
irreps of the point group C2h (for the elements indicated in Table 6.2). The stars
of all four wave vectors considered are single rayed. Therefore the indicated
small irreps are at the same time the full irreps of the group DG 18. Note that
instead of ai3) the vector a;(3) = a\3) + ai3) may be taken as the first primitive
translation vector. Then the vector BP) in the reciprocal space is replaced by
B~(3) = BP) - B13 ) (Fig. 6.2b) and the plane il by the plane il'. Therefore the
irreps of DG 18 may be also obtained from the irreps of G = Cih corresponding
to the wave vectors lying in the plane il'. In particular the restriction of the
small irreps of the group GB and GA (GD and Gd for the space group G = Cih to
the elements of the group of wave vectors X (S) of the layer group DG 18 gener-
ates the same small irreps of the latter.
6.2.4 Induced Representations of Diperiodic Groups

The theory of induced reps described in Sect. 4.2 for triperiodic space groups G
may be easily applied to diperiodic groups DG. The tables of simple induced
reps of DG may be directly constructed by using this theory.
As was shown, every group DG is related to some space group G and there
is a simple correlation between the irreps of these groups. The simple induced
reps of DG may also be deduced from the simple induced reps of G. Indeed the
Wigner-Seitz cell for DG is a right prism with directrix in the layer plane (a
polygon of a plane Wigner-Seitz cell determined by the primitive translation
vectors at and a2)' The set of Wyckoff positions Q-2 for a group DG is contained
in the set Q-3 for the corresponding group G, since it is determined by the
operations of the group DG c G. The site symmetry groups of the points in Q-2
coincide with those of the corresponding points in Q-3. In reciprocal space the
points of the set K -2 correlate only with the points of the set K -3 in the plane il
Table 6.3. Simple induced representations of the groups G = Cih and DG 18

q f3 r D B Z Y E A C
r S X Y
a a. 1+2+ 1+2+ 1 1 1+2+ 1+2+ 1 1

a. 1-2- 1-2- 1 1 l-r l-r 1 1
c a. 1+2+ l-r 1 1 1+2+ l-r 1 1

au l-r 1+2+ 1 1 l-r 1+2+ 1 1
b a. 1+2+ 1+2+ 1 1 1-2- l-r 1 1

a. l-r l-r 1 1 1+2+ 1+2+ 1 1
d a. 1+2+ l-r 1 1 l-r 1+2+ 1 1

a. l-r 1+2+ 1 1 1+2+ l-r 1 1
(or II'). Hence the table of simple induced reps of DG is deduced from the table
of simple induced reps of the related space group G as follows. It is sufficient to
1) strike out the rows with the simple induced reps of G for the points q which
are not contained in the set Q-2;
2) cross out the columns with those k-vectors which do not lie in the plane II;
3) replace the notations of k-vectors for G by the notations of the corresponding
k-points in the Brillouin zone of DG.
Consider an example. Table 6.3 gives the simple induced reps of the space
group G = Cih. The top left part of the table (separated by thick lines) represents
simultaneously the simple induced reps of the group DG. As the irreps of DG 18
are also related to the irreps of the group G = Cih with wave vectors k(3) in the
plane II' (see Fig. 6.2b) the columns D, B in this part of the table may be
replaced by the columns E, A, respectively. Such substitutions naturally keep
the table of the simple induced reps of DG unchanged.
The two-dimensional space groups and the corresponding layer groups are
isomorphous and therefore have the same sets ofirreps. They also have the same
induced reps and K sets in the Brillouin zone. The Wigner-Seitz cell of a plane
group is a section of the Wigner-Seitz cell of the corresponding layer group. The
sets Q for such groups are also identical. Therefore the tables of simple induced
reps of these groups also coincide.
In the groups DG with the symmetry element (Jh (reflection in the layer
plane) all the states of an energy band are specified according to the parity with
respect to reflection in this plane. Hence in using induced reps it is possible to
consider independently energy bands of different parity even when the energy
bands cross.
The induced reps oflayer groups are useful when analyzing electron density
localization on a crystal surface. Such analysis is important in the study of
chemisorption of atoms and molecules.
Calculations of electron surface states show that often the surface states do
not form an energy band separated from the bulk crystal states bands by an
5 Fig.6.3. Energy bands of surface states

for Si (111) and KCl (100) surfaces
4
5
3
K r x r M
Si (111) KCI (100)
energy gap at any k in the plane Brillouin zone of the group DG. In such a case
the analysis of surface states on the basis of induced reps is impossible.
For illustration let us consider the two following examples: electron states
of perfect Si(111) and KCI(lOO) surfaces. According to calculations in both cases
there exist energy bands of surface states separated at any k in the two-dimen-
sional Brillouin zone from the energy band of the bulk crystal states [6.5]. These
bands are reproduced in Fig. 6.3.
In the case of the Si(111) surface (diperiodic group DG 69 - P3m1) the band
of surface states (half occupied) is related to broken bonds (one per surface
atom) and corresponds to the simple induced rep a(ad (in q-basis) or r l , Kl
(in the k-basis). In the case of the KCI(100) surface (diperiodic group DG 55 -
P4mm) the band of surface states is split out of the upper valence band and,
since the latter is generated by p-type states, is centered on the Cl- ions. The
states of this band span the space of the simple induced rep a(e) (in the q-basis)
or r 5 , M 5 , X 3 , X 4 (in the k-basis). Thus the physical nature of surface states in
both cases is perfectly clear.
6.2.5 Use of Translational Symmetry in the Comparison of Bulk

and Surface Crystalline States
In the preceding subsection we have seen that in order to understand the princi-
pal features of the origin of surface states it is important to know how the energy
bands of a crystal look in terms of the diperiodic specification. The comparison
of bulk and surface states according to the symmetry is based on the relation
between the irreps of the corresponding tri- and diperiodic groups G and DG.
The bulk states are specified by the wave vector k in the three-dimensional
Brillouin zone (BZ-3) for the group G. The surface states are classified by k in
the two-dimensional Brillouin zone (BZ-2) of the layer (planar) group DG.
The choice of the translation vectors a1 and az in the surface plane depends
on its orientation relative to the primitive translation vectors a1 3 ) (i = 1,2,3) of
the corresponding space group G. However, due to reconstruction of the surface
layer its translational symmetry may change with respect to that of a perfect
section. When the reconstruction effects may be neglected the symmetry group
DG of a crystal with a surface is a subgroup of the bulk crystal group G.
Fig. 6.4. Brillouin zone for space groups Civ and DG-56
(BZ-2 is hatched)
The procedure of respecification of states is simplest in the particular case

when the basic translation vectors a\3) and a~3) are in the surface plane and the
vector a~3) perpendicular to it. Then the vector B~3) of the reciprocal lattice for
the group G is perpendicular to the plane of the vectors BP) and B~3), which are
at the same time unit cell vectors in the reciprocal space of the diperiodic group
DG. The BZ-2 is a section of the corresponding BZ-3. In this case the projection
k II of any wave vector k(3) from BZ-3 onto the plane of BZ-2 is always inside of
BZ-2. The dispersion law E = En(k(3 in terms of the wave vector kll in BZ-2
takes the form
(6.2.9)
Let us take as an example the space group G = clv (P4bm). The surface (001) is
perpendicular to the basic vector a~3) of the simple tetragonal lattice. The corre-
sponding layer group DG 56 (P4bm) has a square planar lattice. The BZ-2 is a
horizontal section of BZ-3 (Fig. 6.4).
In general, the respecification of electron states and energy levels is more
complex. Consider, for example, crystals with face-centered cubic Bravais lat-
tices. Many semiconductors and dielectrics have lattices of this type. For the
surfaces (001), (110) and (111) the lattices are square, rectangular and hexagonal,
respectively. The basic translation vectors of the direct and reciprocal lattices
for these three cases are given in Table 6.4 (al and a2 are given in units aj2, B;
in units 2nja, where a is the edge of a simple cubic cell).
Table 6.4. Vectors of basis translations for three

sections of a face-centered cubic Bravais lattice
Surface: (001) (110) (111)

Translation
vectors
a, 110 -110 1-10

"2 1-10 002 10-1
B, 110 -110 2/3, - 4/3, 2/3
B2 1-10 001 2/3,2/3, -4/3
Fig. 6.5. Brillouin zones for a face-centered cubic lattice and surfaces (aJ (001), (b) (110), (e) (111)
We see that the vectors Bi (i = 1,2) are now not the translation vectors of
the three-dimensional reciprocal lattice. Therefore the boundaries of BZ-2 do
not coincide with those of BZ-3. Figure 6.5 shows the Brillouin zones corre-
sponding to the surface (001), (110) and (111) inscribed in the three-dimensional
Brillouin zone for a face-centered cubic lattice. Note that some nonequivalent
points of BZ-3 become equivalent in BZ-2 [for example, the points X for the
surface (001) and the points L for the (110) surface]. Some points of BZ-2 have
higher symmetry than in BZ-3 [for example, the vertexes of BZ-2 for (111) sur-
face]. These properties of BZ-2 arise because the unit cell vectors in the
reciprocal space B; are not the lattice vectors of the three-dimensional
reciprocal lattice.
To obtain the crystal energy band structure in terms of a diperiodic specifi-
cation it is necessary to represent the dispersion law E = En (k(3) in the form
(6.2.10)
where kll is a projection of the wave vector k(3) onto the surface and kl. is its
component perpendicular to the surface. The vector B" is assumed to be chosen
so that the wave vector k~ = k II + B" takes values in the limits of BZ-2.
The dispersion law E~(kD = En(k~ + kl. - B.) for the upper valence and
low conduction bands of MgO crystal along the symmetry directions of BZ-2 is
shown in Fig. 6.6, the unreconstructed surface is formed by the section plane
(001). We see from Fig. 6.6 that in the projection of the energy bands of the
three-dimensional crystal on the two-dimensional Brillouin zone there are for-
-
~
r L M x
~
r Fig. 6.6. Surface and bulk states in the MgO crystal [6.8]
bidden energy lacunas. When the surface is taken into account, a band of sur-
face states appears inside the energy lacuna. These surface states are analogous
to the local energy levels of point defects which appear in the forbidden energy
gap. The energy levels of surface states may arise in the continuous energy
spectrum of a bulk three-dimensional perfect crystal (Fig. 6.6). These are the
so-called resonance surface states. They are analogous to the point defect
states in the spectrum of bulk crystal states.
7. Application of Induced Representations
of Space Groups to Second Order Phase Transitions
Group-theoretical methods have proven to be very useful in the analysis of the symmetry changes
in solid state continuous (second order) phase transitions [7.1, 2] and have been systematically
applied to a large number of systems [7.3]. The Landau theory of continuous phase transitions is
the basis of this symmetry analysis [7.1]. Symmetry rules used in the Landau theory are briefly
reviewed in the next section.
7.1 Symmetry Rules in the Landau Theory

of Second Order Phase Transitions
Consider a continuous phase transition between two crystalline phases. Let the
higher-symmetry phase have the symmetry of the space group Go and let G be
the space group of the lower-symmetry phase. For a continuous phase transi-
tion a subgroup criterion is introduced, i.e., it is supposed that G is a subgroup
of Go (G c Go). Let the density function p(r) be written
p(r) = po(r) + L 17i fMr) . (7.1.1)

i
In the higher-symmetry phase the order parameter '1(17 1, ... ,17m) equals 0 and
thus p = po(r). In the lower-symmetry phase 'I does not equal 0 but the Landau
theory requires that the components 17i of the order parameter belong to the
same irrep of the space group Go (single irrep criterion).
The irrep (*k, y) of Go which drives the transition must subduce the unit
irrep (0,1) of the lower-symmetry phase group G (subduction criterion). By
definition, the lower-symmetry phase density function (7.1.1) must be invariant
under all the operations 9 E G, i.e., gp(r) = p(r). Since G c Go the function po(r)
satisfies this condition. Thus the subduction criterion means that the particular
linear combination Li 17iJi(r) of basis functions Ji(r) must be a basis function of
the unit irrep of G. This is possible only if (*k, y) 1G contains the unit irrep of G.
The number of times that (*k, y) subduces the unit irrep is given by r 1 =
nc/ L9EGX<*Y)(g). The subduction frequency r 1 # 0 is the number of inde pen-
dent vectors 'I which are invariant under all the operators 9 E G (g'l = 'I). The
group G is called an isotropy subgroup of Go.
Any subgroup G' eGis also an isotropy subgroup of Go. However, Landau
theory allows only those G' for which r 1 (G') > r 1 (G) holds, i.e., if there exists

206 7. Application of Induced Representations to Second Order Phase Transitions
some additional '1 which is left invariant under the operations in G' but not
under all the oprations in G (chain criterion).
The subduction and chain criteria are necessary and sufficient to identify
isotropy subgroups of a space group for any of its irreps. A systematic method
of generation of isotropy subgroups is developed in [7.4J and applied to
diperiodic and triperiodic space groups [7.2, 5]. This method does not require
the matrices D(g) of the reps. One needs only their characters X(g).
Further selection of isotropy subgroups is made by using the Landau and
Lifshitz conditions [7.1]. These conditions select irreps which may be active in
a continuous transition. The order parameter" corresponds to a physical quan-
tity, which has to be real even when the irrep itself may not be. Therefore, only
a physically irreducible irrep (*k, y) + (*k, y)* = (*k, Y)phys must be considered as
active. The Landau condition is related to the stability of the high-symmetry
phase at the transition and states that the symmetrized third power of (*k, Y)phys
must not contain the identity rep of Go:
nG~ L EtX(g3) + h(g)x(g2) + h 3(g)] = 0 (7.1.2)

geG o
When (7.1.2) holds no third order invariant terms can appear in the free energy
expansion over degrees of order parameter ".
The Lifshitz condition tests the stability of the lower-symmetry phase and
ensures that the lower-symmetry phase is a crystal phase commensurate with
the higher-symmetry phase. This condition means that the anti symmetric
double product of (*k, Y)phys cannot contain the vector repx v (g):
nG~ L iEX2(g) - X(g2)Jxv(g) = 0 (7.1.3)

geG o
Only irreps associated with symmetry points of the Brillouin zone can satisfy
the Lifshitz condition. Note that some of the irreps associated with the symme-
try points may also fail the Lifshitz condition. Even after restricting by the k
points of symmetry one obtains more than 4000 irreps among the 230 space
groups. More than 15000 isotropy subgroups were obtained for these irreps
[7.2]. These results provide information about possible phase transitions allowed
by the Landau theory.
At this level of analysis no information about the crystalline structure is
used. This information becomes necessary when the tensor field criterion is
introduced: the irrep (*k, Y)phys driving the phase transition must be contained
in a tensor field rep D ~F of a parent space group Go [7.6,7]. By definition,
the tensor field rep is ; direct product of a tensor rep D~ and of a per-
mutation rep D~o of the atoms of the crystal: D~F0 = D~0 xh~0 .
The basis functions of the tensor rep DJo are components of a tensor and
remain invariant under the translational part of the space group operations, i.e.,
it is the rep of the space group Go with the wave vector k = 0 and, in the general
7.2 Tensor Fields in Crystals and Induced Representations of Space Groups 207
case, is a sum of several irreps of the point group Fo of the space group
Go (T = Li yJ The tensor in question describes some physical property of the
crystal.
The permutation rep D~o shows how the crystal atoms permute under space
group operations. In lattice vibrational problems (displacive phase transitions)
one considers the vibrational tensor field rep D"G o x D~0 where DaT0 = D"G0 is a
polar vector rep of a space group describing the transformation properties of the
atom displacements in a crystal. In Chap. 8 this tensor field rep is considered in
analyzing the symmetry of phonons in crystals.
When determining the possible types of magnetic ordering in crystals one
uses DJ o = D~o' the axial vector rep. In the case of magnetostructural phase
transitions in crystals with strong spin-lattice coupling, the tensor transforming
according to the rep DJo = D"G o x D~o is assumed to be known at the positions
of the atoms.
Lastly, in order-disorder phase transitions the basis function of DJ o is a
scalar and transforms acccording to the identity rep of the space group Go.
The permutation rep D~o is the same for all tensor field reps defined on the
crystal. Moreover, a crystal of space group Go can be partitioned into "simple
crystals". Each simple crystal consists of all atoms whose atomic position vec-
tors can be obtained by applying all elements of the space group Go to anyone
atomic position, generating the "simple crystal" [7.7]. Comparing this definition
with that of orbit (Sect. 3.4.1) we can see their equivalence. No two simple
crystals have atoms in common (the elements of Go permute the atoms of each
orbit among themselves) so that D~o is the direct sum of the D~~ (i = 1,2, ... , n)
for orbits or WyckoiTpositions occupied by atoms. In [7.7] the theory of induced
reps is used to determine all space group irreps contained in D~o' The tensor
field rep DJ~ is reduced then to irreducible components using the DJ~ direct
product form. This procedure is lengthy and must be done for all crystal struc-
tures considered. The tensor field rep reduction is significantly simplified if one
takes into account the connection between the tensor field rep and induced rep
of space groups [7.8]. This connection is considered in the next section.
7.2 Tensor Fields in Crystals and Induced Representations

of Space Groups. Tensor Fields for Space Group D!!
The basis functions of the tensor field rep are the components of some tensor
field defined on the atoms of a crystal. This basis may be obtained by the
induction procedure from the tensor reps ~ of the site symmetry groups Gj
corresponding to the Wyckoff positions qj occupied by symmetrically in-
equivalent atoms in the crystal.
If Tj = L JJ)il [fl)il are the irreps of OJ contained in 1j 1 the tensor field
rep is a direct sum of induced reps (qj,flY),
(7.2.1)
The induced rep (qj, PY is a simple one (if qj E Q) or a direct sum of simple ones
(if qj Q; Sect. 4.2.3):
(7.2.2)
In (7.2.2) it is assumed that qJ is one of the points in the set Q for which the
site symmetry group GJ contains Gj as a subgroup (Gj c GJ ). The numbers rJii)
are the coefficients in the direct sum giving the rep of the site symmetry group
GJ (qJ E Q) induced from the irrep PY> of its subgroup G/
PJ!i) i GfJ ="L.. r(ij)f3(I)

I J . (7.2.3)
I
In (7.2.3) PY) are the irreps of the site symmetry group GJ

Hence any tensor field rep may be considered as a direct sum (7.2.1) of
several simple induced reps, and its irreducible components are easily found
from the tables of the simple induced reps and the compatibility relations for the
space group Go. The permutation rep D~o is a particular case of DJ: (7.2.1) when
PJi) are the identity irreps of the site symmetry groups Gj of the sites % occupied
by the crystal atoms.
As an example we consider the tensor field rep for a rutile structure (space
group Dlh). The simple induced reps of this space group are given in
Table 4.5; the short notation for the rutile structure is Dl:[aDzh(Ti),fCzv(O)].
As is seen from Table 4.5, the Wyckoff position f occupied by oxygen atoms
does not belong to the set Q.
The permutation rep for titanium atoms Dii is found directly from Table 4.5
as the simple induced fep (a, ag ) in the k-basis:
DP(Ti) = (a, ag )
(7.2.4)
To find the permutation rep for oxygen atoms D~ = (f,a l ) we take into
account that induced rep a l (Czv)i DZh is equal to ag + b3u (Table 4.2). Therefore
the permutation rep D~ = (f, ad = (a, ag ) + (a, b3u ) is a composite one. Now its
symbol in the k-basis is directly found from Table 4.5:
D~ = (f,a 1 ) = (a,a g ) + (a,b 3u ) = r(I+,4+,5-), M(l+,4+,5-),
Z(I,4), A(I,4), X(2,2), R(l +,1-) . (7.2.5)
When analyzing the symmetry of order-disorder phase transitions con-

nected with titanium or oxygen atoms one considers only those irreps of the
high-symmetry phase space group Dl: which are contained in (7.2.4) and (7.2.5),
respectively. In Table 7.1 we give isotropy subgroups for r-point irreps taken
7.2 Tensor Fields in Crystals and Induced Representations of Space Groups 209
Table 7.1. Isotropy subgroups of second order phase transitions

for the parent group D~: and the r-point of the Brillouin zone.
From [7.2]
Irrep Isotropy subgroups Irrep Isotropy subgroups

r,+a
1
D'4
4h r,- D~
1
r+
2
D'2
2h r-
2 D~d
r/ clh r3- c1v
r+4
'9
D2h r:-
4 D~d
r,+
5 Cih' Cih' Ci r,-
5 C]v, CJ:, csl
a Landau condition is not satisfied.
from [7.2]. Taking into account (7.2.4) one concludes that for order-disorder
phase transitions connected with titanium atoms the space group of the lower-
symmetry phase is Di% for active irreps connected with the r-point of the
Brillouin zone.
To analyze displacive second order phase transitions for rutile Ti0 2 one
has to consider the vibrational tensor field rep. The titanium atom contribution
D; to the vibrational tensor field rep may be found directly from Table 4.5: the
displacements of these atoms form the bases of the a-site symmetry group D2h
irreps: x - b3u , Y - b2u , Z - b1u ' Hence the vibrational tensor field rep is com-
posite:
(7.2.6)
The contribution of oxygen atoms to D;, the vibrational tensor field rep,
may be found after preliminary induction from irreps a 1 , b1 , b2 of the f-site
symmetry group C 2v to the a-site symmetry group D2h : a 1(C2v )i D2h = ag + b3u ,
bl(C2v)iD2h = b39 + b 1u , b2(Czv)iD2h = b 19 + b2u ' The irreps a 1, b1, b2 corre-
spond to the symmetry of the oxygen atom displacements along the x - y,
x + y, and z-directions, respectively. Hence
(7.2.7)
Using (7.2.6, 7) one obtains from Table 4.5 the contribution of the rutile struc-
ture at the symmetry points of the Brillouin zone in the vibrational rep. For
example, at the r-point of the Brillouin zone one has
Dfi(r) = r2- + r3- + 2rs- ;

(7.2.8)
m~=~+~+~+~+~+~+~+~
Using (7.2.8) one selects those isotropy subgroups for the r-point from Table 7.1
which correspond to irreps Dfi or Do.
When determining the possible types of magnetic ordering of Ti atoms one
uses DJo = D~o' the axial vector rep. For the titanium a-site symmetry group
D2h this rep is b 19 + b2g + b3g so that at the r-point of the Brillouin zone one
obtains from Table 4.5:
(7.2.9)
7.3 Vibrational Field Representation and Phase Transitions

in High-Temperature Superconductors
Use of induced rep tables allows one to immediately find tensor field reps for
crystals with many atoms in the primitive unit cell when the usual factor group
analysis [7.9] is too cumbersome. The induced rep method is especially effective
when several crystals with the same space group Go must be treated. As an
example we consider some crystalline high-temperature (high- 7;,) superconduc-
tors with the symmetry space group Go = DJ; (I4/mmm). The atoms occupy the
following positions in the crystal [7.10]:
La 2Cu0 4-aD4h (Cu), cD2h(01), eC4v (La,02) ; (7.3.1a)
CaBi2Sr2Cu20s-bD4h(Ca), eC4v (Bi, Sr, Cu, 02, 03), gC2v (01); (7.3.1b)
Ba 2TI2Cu06-aD4h(Cu), cD 2h (01), eC4v (Ba, Tl, 02, 03) . (7.3.1c)

The atomic displacements in these crystals form the bases of the following site
symmetry group irreps: x, y-e u, z-a 2u for atoms in Wyckoff positions a and
b (G, = D4h ); x-b3u , y-b2u , z-b 1u for atoms in position c (G, = D2h ); x,y-e,
z-a 1 for atoms in position e (G, = C4v ); x-b 1, y-b 2, z-a 1 for atoms in
position 9 (G, = C2v )' Hence, the contribution D(q) of the displacements of
atoms in these positions q in the vibrational tensor field rep of the corre-
sponding crystals is
D(a) = (a, eu + a 2u ) ; (7.3.2a)
D(b) = (b, eu + a 2J ; (7.3.2b)
D(c) = (c, b3u + b2u + b1u ) ; (7.3.2c)
D(e) = (e,e + ad = (a,eg + eu + a 1g + a 2J ; (7.3.2d)
D(g) = (g,b 1 + b2 + ad
(7.3.2e)
Equations (7.3.2) give induced reps of the space group DJ; for positions
occupied by atoms in the q-basis. To obtain their indices in the k-basis one
uses Table 4.20 of the simple induced rep of this space group. The information
7.3 Vibrational Field Representation 211
obtained may be used both for analysis of the phonon symmetry (Chap. 8) and
second order phase transitions.
The crystal YBa2Cu307' in its high-temperature superconducting phase,
has the symmetry group Go = Dih(Pmmm) [7.10]. The atoms occupy the
following positions: aD 2h (Cul), eD 2h (01), hD2h (Y), qC2v (Cu2,04), rC 2v (03),
sC2v (02), tC2v (Ba). The displacements of atoms transform according to the reps
of site symmetry groups G,: x-b 3u ' y-b2u , z-b 1u for atoms in positions q '" a,
e, h (G, = D2h ); X-bl' y-b2, z-a l for atoms in positions q '" q, r, s, t
(G, = C 2v )' The contribution D~ of the displacements of the atom A of the
crystal to the vibrational tensor field rep is
(7.3.3a)
(7.3.3b)
(7.3.3c)
= (a,b2g + b3u + b3g + b2u + ag + b1U> ; (7.3.3d)
D~)3 = (r, bl + b2 + at>

(7.3.3e)
= (b, b2g + b3u + b3g + b2u + ag + blu) (7.3.3f)
D~a = (t,b l + b2 + at>

(7.3.3g)
Tables 4.23 of the simple induced rep of the space group Dih gives the irreduc-
ible components of these reps (for k E K). As seen from Table 4.23, the Wyckoff
positions a, e, h are included in the set Q so that using this table and (7.3.3a-c)
one directly finds the vibrational tensor field reps for CuI, 01, and Y atoms. The
rest of the positions occupied by atoms (q, r, s, t) are not included in the set Q.
Equations (7.3.3d-g) are obtained using the induction procedure from irreps of
Table 7.2. Tensor field vibrational representation for oxygen

atoms at the X-point of the Brillouin zone (La 2 Cu0 4 structure-
space group Din
X X
cD 2h {Ol) blu{z) 3+4+ eC4v (02) at{z) l+r

b3u {x) 1+2+ e{x,y) 34
b2 .{y) 1+2+
the C Zv site symmetry group. Here, it was taken into account that the site
symmetry groups of q, r,s, t positions are differently oriented relative to the
space group Dih symmetry elements, so that these Czv-type groups are sub-
groups of different Dzh-type groups (G q eGa, G r C Ge , Gs C Gb, G t C Gh ).
Using (7.3.3) and Table 4.23 one can find the symmetry of phonons in
YBa 2 CU 3 0 7 and, using the table of isotropy subgroups for the parent group
Dih from [7.2], the possible displacive phase transitions. From this table one
also easily obtains permutation rep components for different groups of atoms.
For example, DP(Cu1) = (a, ag ), DP(01) = (e, ag ), DP(y) = (h, ag ).
As an example of the application of the induced reps in the symmetry
analysis of second order phase transitions we consider the phase transition in
(La 2 _ x Srx )Cu0 4 involving a tilt of the oxygen octahedron about the [110]
direction of the tetragonal parent cell. The higher-symmetry space group Go =
Dl; corresponds to a tetragonal structure, the lower-symmetry space group is
found to be G = Di2 (Cmca). The ratio of sizes of the primitive unit cell in the
tetragonal parent group to the orthorhombic subgroup was found to be 12. It is
known that the second order axis in the lower-symmetry phase is directed along
the translation vector a; = 2a3 + a 1 + a 2 (where ai' i = 1, 2, 3 are the basic
translation vectors of the tetragonal lattice); these are the oxygen atoms which
shift during the phase transition. Therefore we consider the tensor field rep
generated by oxygen displacements (7.3.2c, d). Using the isotropy subgroups
table for the parent group Dl; from [7.2] and the information about the transi-
tion vector a; of the orthorhombic phase and the relative size of primitive cells
in the two phases, one concludes that the possible irreps driving the phase
transition into the orthorhombic phase are X t , X}, X f , xi. All these irreps
satisfy the Landau and Lifshitz conditions. In Table 7.2 the tensor field vibra-
tional rep for oxygen atoms at the X -point of the Brillouin zone of the parent
space group Dl; is given. It is seen that the tensor field criterion excludes from
consideration the Xl irreps. In addition, the phase transition connected with
the displacement of both 01 and 02 oxygen atoms has the symmetry Xj, X;.
From isotropy subgroups tables it follows that these irreps drive the phase
transition with the lower-symmetry space group Di2 or Di~. This conclusion is
verified by experimental data [7.11].
8. Induced Representations of Space Groups
in Phonon Spectroscopy of Crystals
The use of the site-symmetry approach in lattice dynamics allows one to make a quick group-
theoretical analysis of the phonon symmetry not only at the Brillouin-zone center but in the entire
Brillouin zone. To demonstrate the efficiency of this method for crystals with many atoms in the unit
cell we have considered the symmetry of the phonon states in high-temperature superconductor
crystals. Bearing in mind the considerable current theoretical and experimental interest in the
study of semiconductor super lattices we consider selection rules due to phonon symmetry and op-
tical spectra for the semiconductor superlattices (GaAs)m(AIAs)n and (Si)m(Ge)n.
8.1 Phonon Symmetry Analysis
The complete group-theoretical analysis of phonon symmetries of complex

crystals with a large number of atoms per primitive cell has received consider-
able attention in recent years. This is because knowledge of the symmetry of
phonons at k # 0 is necessary for interpretation of second order infrared and
Raman spectra. Furthermore, this information can be used in the symmetry
assignment of vibrational mode branches calculated by numerical methods.
The usual method [S.l ~ 3] of phonon symmetry analysis employs the con-
struction of the rep of the space group of a crystal in the space of atomic
displacements, called full mechanical rep, with its subsequent decomposition
into irreps of the group. It is very complex, especially for phonons with k # o.
Although the method given in [S.3] is simpler, because instead of summation
over all the atoms in the primitive cell summation over the atomic groups with
the same site symmetry is performed, it remains rather complicated.
Here we use the method of induced reps of space groups to analyze the
symmetry ofphonons. For complex crystals this method has proven to be much
more effective [S.4] than the traditional ones. As was shown in Chap. 4, the
generation of the induced reps for a space group G does not involve the specific
arrangement of atoms in the primitive cell. Combining the induced reps gener-
ated with the independently established data on the atomic arrangement one
can easily obtain the full mechanical rep. Hence, this method is especially effec-
tive for crystal families having the same space group but differing in the distribu-
tion of atoms among the Wyckoff positions.
The procedure of analysis of the phonon symmetry is the following. First,
for the space group G of a given crystal the simple induced reps are generated.
Second, using the simple induced reps together with the compatibility relations
and arranging atoms in the primitive cell over the Wyckoff positions one can
determine the symmetry of the phonons. Only those of the induced reps which

214 8. Induced Representations of Space Groups in Phonon Spectroscopy of Crystals
Table 8.1. Phonon symmetry in rutile Ti0 2 crystals with space group Dl:
q p r M Z A X R
Ti(2a) bJu(z) 2-,r 2-,3- 1 1 1 1-

(0 0 0) b2u (x - y) 5- 5- 3 3 2 1-
D2h b3u (x + y) 5- 5- 4 4 2 1
O(4f) aJ(x + y) 1+,4+,5- 1+,4+,5- 1,4 1,4 2,2 1+, 1-
(x x 0) b2 (x - y) 2+, 3+, 5- 2+,3+,5- 2,3 2, 3 2,2 1+, 1-
e2v bJ(z) 2-,3-,5+ 2-,r,5+ 1,3 1,3 1, 1 1+, 1-
are induced by the irreps of the site symmetry groups according to which the
components of the vectors of the local atomic displacements transform are used.
As an example, in Table 8.1 the phonon symmetry in rutile crystals is given.
The results given are easily obtained from Table 4.5 of simple induced reps of
the space group Dl: and the atomic arrangement in rutile Ti0 2 .
Next, using the found symmetry of the phonons one can establish which vibra-
tional modes are active in the first and second order infrared and Raman spectra.
8.2 Infrared and Raman Spectra Selection Rules
The symmetries of infrared and Raman-active phonons are governed by selec-

tion rules following from the symmetry restrictions imposed on matrix elements
of transitions from an initial vibrational state to a final one under the action of
the perturbation operator W In terms of group theory, for a system having the
space group G, the transition matrix elements do not vanish due to symmetry if
the following Kronecker product of reps of G contains the identity rep
(8.2.1)
Here DI and Di are the reps of the space group G according to which the initial
and final states are transformed, D W is the rep according to which the perturba-
tion operator W is transformed and r 1 is the identity rep of the group G.
Under standard experimental conditions, the initial state is always the
ground state and transforms as the identity rep of the group G. Hence, (8.2.1)
reduces to
(!U.2)
In infrared absorption, the perturbation operator W is the derivative of the
dipole moment and, therefore, it transforms as the vector rep D" of the space
group G. In nonresonant Raman scattering, the operator W is a symmetric
polarizability tensor of second rank. Hence, it transforms as a symmetrized
square of the vector rep [D"]2 of the group G.
Thus, in infrared spectra the allowed final states obey the condition
DI (lD" =I 0 (8.2.3)
8.3 Phonon Symmetry and Optical Spectra Selection Rules in Semiconductor Superlattices 215
whereas in Raman spectra the allowed final states obey the condition
Df n [D"Y =F 0 . (8.2.4)
In first order optical processes, the final states Df transform as the irreps of
the space group G with k corresponding to the r-point (k = 0) of the Brillouin
zone. This follows from the momentum conservation law and is justified since
the wave vectors of the incident and scattered photons are much less than the
phonon wave vectors corresponding to the Brillouin zone boundary.
In second order optical processes, the final states Df transform as the
symmetrized square of the irreps [D~kl]2 of the space group G (for overtones),
or as a Kronecker product of the irreps D{kl x D{kl for phonon combinations
of the same symmetry, or as D{kl x D{kl for phonon combinations of different
symmetries. Since the reps according to which the perturbation operator W is
transformed correspond to the zero wave vector, only those phonon combina-
tions for which the Kronecker product of corresponding irreps contains the rep
with k = 0 can be active.
In addition, only those phonon modes which correspond to critical symme-
try points of the phonon density of states function may appear in second order
infrared and Raman spectra. For the jth vibrational mode transforming as the
irrep ,~) of the little group Gk , the k-point of the Brillouin zone is a critical
symmetry point if the following Kronecker product of reps does not contain the
identity rep (Sect. 5.3.4):
(8.2.5)
where ,(1) is the identity rep for the little group Gk and ," is the vector represen-
tation of the little co-group F k . It has been shown that little co-groups allowing
the existence of critical symmetry points are groups with inversion symmetry as
well as point groups 1d, 0, T, D 2d , D 3h , Dn , S4, C3h [8.3].
8.3 Phonon Symmetry and Optical Spectra Selection Rules

in Semiconductor Superiattices
New techniques (e.g., molecular beam epitaxy) allow fabrication of artificial

single crystals AmBn with varying primitive cells. These are called superlattices
and consist of alternating ultrathin layers of materials A and B, where m
and n are the numbers of monolayers of the corresponding materials in the
superlattice primitive cell. To date the most investigated superlattices are
(GaAs)m(AIAs)n[OOl] and (Si)m(Ge)n[OOl] systems [8.5-11] due to their impor-
tance in semiconductor device applications. These systems are also within the
scope of our discussion since superlattices are ideal systems enabling demon-
stration of the advantages of the site symmetry approach to lattice dynamic
problems.
F or each pair of materials A and B the superlattices grown along the [hkl]
direction constitute a few single crystal families specified by G1 , G2 , ... , Gs space
groups depending on m and n. Each member of a crystal family has the same
space group but differs from the other members in the atomic arrangement over
the Wyckoff positions, which is also governed by the specific values of m and n.
For such families, the site symmetry approach has proven to be very effective. It
enables one to treat each crystal family as an entirety since the generation of the
induced reps does not involve the distribution of atoms in the primitive cell over
the symmetry positions.
8.3.1 (GaAs).,(AIAs). Superlattices

The (GaAs)m(AIAs)n superlattices grown along the [001] direction constitute
two single crystal families specified by the space groups Did (m + n = 2k) and
Did (m + n = 2k + 1) depending on whether the total number of monolayers
(m + n) per primitive cell is even or odd (8.5, 8.7).
It has been established that not only space group symmetry but also the
atomic arrangement over the Wyckoff positions in the primitive cell is governed
by the specific values of m and n, as mentioned above [8.8]. Thus, in terms
of symmetry, superlattices belonging to the same family are distinct crystals
differing in their atomic arrangement.
The general formulas for the atomic arrangement in (GaAs)m(AIAs)n[OOl]
superlattices for different combinations of m and n are presented in Table 8.2
[8.8]. The corresponding atomic structures are shown in Figs. 8.1,2.
Having established the atomic arrangement over the Wyckoff positions
(Table 8.2) and using the simple induced reps of the space groups Did and
Did (Chap. 4) together with the compatibility relations, one can determine the
phonon symmetry at corresponding points of the Brillouin zone for a super-
lattice with arbitrary m and n. Thus the method allows one to obtain the
phonon symmetry without needing to generate the full mechanical rep for each
superlattice all over again, as is usually the case.
The phonon symmetry for (GaAs)m(AIAs)n[OOl] superlattices is presented
in Tables 8.3, 4. Tables 8.3 and 8.4 allow one to establish which atoms
and which local atomic displacements contribute to the modes with a given
symmetry.
This method is especially effective for ultrathin superlattices with m, n ~ 7
since in such cases a full separation of contributions of particular atoms into
given normal modes becomes possible. By monitoring the corresponding lines
in the Raman and infrared spectra one can glean information about the corre-
sponding sublattice. This information could be used, e.g., to optimize the growth
conditions for higher quality superlattices.
For example, for the (GaAs)l (AIAs)l superlattice the vibrational modes
with symmetry r l , M l , M 4 , A l , A3 involve only the contributions from the
displacements of the As atoms in the g-positions. Hence, the corresponding
spectral lines are due only to the As sublattice.
In the (GaAs)1 (AI Ash superlattice the vibrational mode with symmetry r l
involves the contributions from the As atoms in g-positions and the contribu-
Table 8.2. Atomic distribution over Wyckoff positions in (GaAs)m(AIAs). superlattices. The numbers preceding the 00
chemical element symbols denote the number of such atoms at the Wyckoff position shown in parentheses w
Space group Did (m + n = 2k), m .:;; n
d1
o
:::
o
:::
m = 2k + 1, n = 2s + 1 m = 2k, n = 2s rJl
m = 4i + 1 m=4i+3 m = 4i + 1 m = 4i + 3
n=4j+3 n = 4j + 1 n=4j+l n=4j+3 m + n = 4i m + n = 4i + 2
I
Q

IGa(a) mGa(g) c.
(m + n)As(g) nAI(g) o
lAs(a) g.
lAI(d) lAI(e) e:..
rJl
m -1 m+ 1 m -1 m+ 1 ~
-2- Ga(f) -2- Ga(f) -2- Ga(f) -2- Ga(f) lAs(d) lAs(e) ;
m -1 m- 3 m -1 m- 3
~
-2- Ga(e) --Ga(e) --Ga(e) -2- Ga(e) (m+n)
-2- As(f) (m+ n
-2--1 ) As(f) a.o
2 2 :::
n- 1 n- 1 n-3 ~
n; 1 Al(f) -2- A1 (f) -2- A1 (f) -2- A1(f) (m+
-2-n - 2) As(e) (m+ n
-2--1 ) As(e) c
[
n-3 n- 1 n-l n+ 1 s
-2- A1(e) -2- A1(e) -2- A1(e) -2- A1(e)
Space group Did (m + n = 2k + 1)

r
[
~o
m = 2k + 1, n = 2s m = 2k, n = 2s + 1 ....
rJl
IGa(a) lAs(e) nAl(e) lAs(a) lAl(e) mGa(f) ~::!.

(m - I)Ga(e) (m + n - I)As(f) (n - l)Al(f) (m + n - I)As(e) a
'
en
~
-.J
,.
(b) (Ga AS)1 (AI AS)3
A
r
r(
,""
----
-- -----
...----.
AI (1d)
i/ 0 /
, ,
-"C-
t7
,, As (2g) (e) (Ga AS)2 (AI AS)2
---
V AI (21) AI (2g)
---- - - 7
.... V
,e As (2g) As (2fj
1"-- -----
(a) (Ga AS)1 (AI Ash CI3

/
,,

---
---
,,
,
Ga (1a)
As (2g)
Ga (2g)
As (1a)
l)
,- V
AI (1c) AI (21)
-----

--- a3
As (2g) , As (2g) As (2f)
-----
Ga (1a) V 0 1/
CI3
As (2g) ---"--,
,:~ ....,... --- " \.
,
AI (2g)
As (1d)
a2 (/ Va2 a2
/
a1 /'
a,
Fig.8.la,b. Crystal structure of (GaAs)m(AlAs)n [001] superiattices with space group D~d'
(a) m = 1, n = 1; (b) m = 1, n = 3; (c) m = 2, n = 2
(Ga Ash (AI AS)2
./ ./
,:! ~~~~-~ ~.
/OV AI (2e)
----. --
As (1c)
D~---G
1/ V Ga(1a)
-----e- --
/ / As (21)
1<0'-- *---
,-
V _____ ~
,"
Fig. 8.2. Crystal structure of the (GaAs)l(AlAsh [001] super-

lattice with space group D~d
Table 8.3. Phonon symmetry in (GaAs)m(AlAs)n[O 0 I] superlattices with space group DId (P4m2)
m=lm=2m=lm=lm=2m=3 q p r M A Z X R
n = I n=2 n=3 n=5 n=4 n=3
IGa lAs IGa IGa lAs IGa la b2 (z) 2 2 2 2 I I

(000) e(x,y) 5 5 5 5 3,4 3,4
Du
IAI - - IAI lAs IAI Ie b2 (z) 2 3 4 I 3 3
(t t t) e(x,y) 5 5 5 5 1,2 1,2
Du
- lAs IAI - - - Id b2 (z) 2 2 I I I I
(00 t) e(x,y) 5 5 5 5 3,4 3,4
Du
- - - 2AI 2As 2AI 2e a,(z) 1,2 1,2 1,2 1,2 I, I I, I
(00 z) b2 (y) 5 5 5 5 3,4 3,4
C2v b,(x) 5 5 5 5 3,4 3,4
- 2As 2Al 2Al 2As 2Ga 2f a,(z) 1,2 3,4 3,4 1,2 3,3 3,3
(t t z) b2 (y) 5 5 5 5 1,2 1,2
CZv b,(x) 5 5 5 5 1,2 1,2
2Ga 2Ga 2g a,(z) 1,2 5 5 1,2 I, 3 1,3

2As 4As 6As 6As
2Al 4Al (0 t z) bz(y) 5 1,2 1,2 5 1,4 1,4
CZv b,(x) 5 3,4 3,4 5 2, 3 2,3
Table 8.4. Phonon symmetry in (GaAs)m(AIAs).[O 0 I] superlattices with space group Did (14m2)
m=lm=2m=lm=1 m=2 m=3 q p r M X P N

n=2 n=3 n=4 n=6 n=5 n=4
IGa lAs IGa IGa lAs IGa la bz(z) 2 2 2 2 I

(000) e(x,y) 5 5 3,4 3,4 1,2
Du
lAs IAI lAs lAs IAI lAs Ie bz(z) 2 I 4 3 I
<i i t) e(x,y) 5 5 1,2 1,2 1,2
Du
2Ga 2e a,(z) 1,2 1,2 1,2 1,2 I, I
2Al 4As 4Al 6Al 6As
4AI (z z 0) bz(y) 5 5 3,4 3,4 1,2
CZv b,(x) 5 5 3,4 3,4 1,2
2Ga 2Ga 2f a,(z) 1,2 1,2 3,4 3,4 I, I

2As 4As 6As 6As
2Al 4Al (z + t z t) bz(y) 5 5 1,2 1,2 1,2
CZv b,(x) 5 5 1,2 1,2 1,2
tions from only those Al atoms which form interfaces (Fig. 8.1b). Thus the
corresponding line in the Raman spectrum is dependent on the structure of the
interfaces.
Tables 8.3 and 8.4 also allow one to determine what changes in phonon
spectra could be expected when an atom of the lattice is replaced by an im-
purity.
Tables 8.3 and 8.4 show that the symmetry types of phonons for all super-
lattices with the same space group are independent of the specific values of m
and n. However, the contributions of the displacements of specific atoms to
phonons with a given symmetry do depend on m and n, since by varying the
number of monolayers we rearrange the atoms among the Wyckoff positions.
Also, the structure of the vibrational rep changes, i.e., the number of normal
modes with a given symmetry changes as well.
If the symmetry of phonons at k of 0 is known, the selection rules not only
for the first but also for the second order infrared and Raman spectra can be
derived. The number of vibrational modes whose combinations can appear in
second order optical spectra significantly increases. Since phonons with a given
symmetry are associated with vibrations of a specific group of atoms, this makes
it possible to obtain many details about the supedattice microstructure.
Using the procedure described in Sect. 8.2 the selection rules for super-
lattices with symmetry Did and D~d may be obtained by a direct calculation or
by using the tables of Kronecker products of space group irreps [8.12].
For supedattices with symmetry Did and D~d' in the first order infrared
spectra the F2 (B 2 ) phonons are allowed in (z) geometry and Fs(E) phonons are
allowed in (x') and (y') polarizations where the x' and y' axes parallel to the
[100] and [010] directions are rotated 45 around the z-axis relative to the basic
translation vectors in the layer plane.
In first order Raman scattering, Fl (Ad phonons are allowed in (x' x') and
(y' y') scattering geometries (the variables in parentheses show the polarization
of the incident and scattered light), the F2 (B2 ) phonons are allowed in (x' y')
geometry while the Fs(E) phonons in (x' z) and (y' z) geometries.
For supedattices with symmetry Did' the following phonon combinations
are allowed in second order infrared spectra:
In second order Raman spectra the allowed phonon combinations in (x' x'),
(y' y'), and (zz) scattering geometries are
[lj]2, lj X lj (j = 1,2) ; [Mj ]2,Mj x Mj(j= 1,2,3,4);

(8.3.2)
[Zj]2, Zj X Zj (j = 1,2) ; [Aj]2, Aj x Aj (j = 1,2,3,4) ,
with the following combinations of phonons also allowed in (x', x') and (y' y/)
scattering geometries:
(8.3.3)
In (x' y') scattering geometry the allowed phonon combinations are
(8.3.4)
For superlattices with symmetry Did' the following phonon combinations

are allowed in the second order infrared spectra:
(8.3.5)
In the second order Raman spectra the allowed phonon combinations in (x' x'),
(y' y'), and (zz) scattering geometries are
K=F,M,P, . (8.3.6)
with the following combination of phonons also allowed in (XiX') and (y'y')
scattering geometries:
(8.3.7)
In (x' y') scattering geometry the allowed phonon combinations are
K=F,M,P. (8.3.8)
These results were used for interpretation of the experimental data in [8.9, 10].
8.3.2 (Si)",(Ge). Superlattices

The (Si)m(Ge)n [001] superlattices constitute five single crystal families with the
symmetries Did (m + n = 4k; m, n odd); Did (m + n = 4k + 2; m, n odd); Dih
(m + n = 4k; m, n even); Di: (m + n = 4k + 2; m, n even), and Dl~ (m + n =
2k + 1) [8.11]. The case m = n = 1 corresponds to the Tl group. The crystal
structures for representatives of all 5 families of (Si)m(Ge)n [001] superlattices are
shown in Fig. 8.3. The corresponding atomic arrangements over the Wyckoff
positions for small values of m and n are given in Tables 8.5-9. Using the same
procedure as in Sect. 8.3.1, the phonon symmetry for all 5 families of (Si)m(Ge)n
[001] superlattices was obtained. The results are presented also in Tables 8.5-9.
The selection rules for first and second order infrared and Raman spectra can be
obtained in the same manner as in Sect. 8.3.1.
8.3.3 Experimental Applications

In this section the results of Sect. 8.3.1 will be used to interpret the first
and second order Raman scattering spectra of the (GaAs)m(AIAs)n superlattices
with specific values of m and n. The Raman measurements were performed
on high quality (GaAsbl(AIAs)6 and (GaAsh(AIAs)18 superlattices grown by
molecular epitaxy and characterized by X -ray diffraction, with interface widths
Ge (4e)
Si (2a)
Si (2a) (c) Sij Ge3
Ge (4e) (b) Si2 Ge2
Ge (21) Ge (1c)
Si (2e) Ge (2g)
Ge (4e) Si (2e)
a3
Ge (4e)
Ge (21)
a1
a'1 a2 a1
(d) Si3 Ge3 (e) Si2 Ge4
Ge (2e)
Ge (2e)
Si (2e)
Si (2e)
Ge (2e)
Ge (2e)
Fig. S.3a-e. Crystal structure of (Si)m(Ge)n [001] superlattices: (a) m = 1, n = 2; space group D!~;
(b) m = 2, n = 2; space group D~h; (e) m = 1, n = 3; space group D~d; (d) m = 3, n = 3; space group
D~d; (e) m = 2, n = 4; space group D~~
8.3 Phonon Symmetry and Optical Spectra Selection Rules in Semiconductor Superiattices 223
Table 8.5. Phonon symmetry in (Si)m(Ge)n [001] superiattices with space group D~d (P4m2)
(m+n=4k;m,nodd)
m = I m = 3 m = I m=l m = 3 q P r M A Z X R
n=3 n=5 n=7 n = 11 n=9
lSi lSi lSi lSi lSi la bz(z) 2 2 2 2 I I

(000) e(x,y) 5 5 5 5 3,4 3,4
D2d
IGe - - IGe IGe Ie bz(z) 2 3 4 I 3 3
(1 1 1) e(x,y) 5 5 5 5 1,2 1,2
D2d
- IGe IGe - - Id bz(z) 2 2 I I I I
(001) e(x,y) 5 5 5 5 3,4 3,4
D2d
- - - 2Ge 2Ge 2e at(z) 1,2 1,2 1,2 1,2 I, I I, I
(00 z) bz(y) 5 5 5 5 3,4 3,4
Czv bt(x) 5 5 5 5 3,4 3,4
- 2Ge 2Ge 2Ge 2Ge 2f at(z) 1,2 3,4 3,4 1,2 3,3 3, 3
(11 z) bz(y) 5 5 5 5 1,2 1,2
CZv bt(x) 5 5 5 5 1,2 1,2
2Si 2Si 2g at(z) 1,2 5 5 1,2 1,3 1,3

2Ge 4Ge 6Ge 1,2 1,2 1,4 1,4
2Ge 4Ge (01 z) bz(y) 5 5
CZv bt(x) 5 3,4 3,4 5 2,3 2,3
Table 8.6. Phonon symmetry in (Si)m(Ge)n [001] superlattices with space group D~d (14m2)
(m+n=4k+2; m, n odd)
m= I m = 3 m = 5 q P r M X P N
n=5 n=3 n = 5
lSi lSi lSi la bz(z) 2 2 2 2 I

(000) e(x,y) 5 5 3,4 3,4 1,2
D2d
IGe IGe IGe Ie bz(z) 2 I 4 3 I
(i
D2d
* 1) e(x,y) 5 5 1,2 1,2 1,2
2Ge 2e at(z) 1,2 1,2 1,2 1,2 I, I

2Ge 2Ge (z z 0) 3,4 3,4 1,2
2Si bz(y) 5 5
Czv bt(x) 5 5 3,4 3,4 1,2
2Ge 2f at(z) 1,2 1,2 3,4 3,4 I, I

2Ge 2Si
2Si (z +1 z 1) bz(y) 5 5 1,2 1,2 1,2
CZv bt(x) 5 5 1,2 1,2 1,2
Table 8.7. Phonon symmetry in (Si)m(Ge).[O 0 1] superlattices with space group Dih (m + n = 4k;
m, n even)
m=2 m =2 m=4 q p r X y Z S T U R
n=2 n=6 n=4
2Si 2Si 2e a,(z) 1+,2- 1 1+,r 1+,2- 1 1+,2- 1 1

2Si
2Ge 2Ge (i 0 z) bz(y) 3+,4- 2 3+,4- 3+,4- 2 3+,4- 2 2
C zv b,(x) r,4+ 1 3-,4+ 3-,4+ 1 3-,4+ 1 1
2Si 2f a, (z) 1+,2- 1 3+,4- 1+,2- 2 3+,4- 1 2

2Ge 4Ge
2Ge (i ! z) bz(y) 3+,4- 2 1+,2- 3+,4- 1 1+,2- 2 1
CZv b,(x) 3-,4+ 1 1-,2+ r,4+ 2 1-,2+ 1 2
Table 8.8. Phonon symmetry in (Si)m(Ge).[O 0 1] superlattices with space group Di:
(m+ n = 4k + 2; m, n even)
m= 2 m =4 q P r X R S T W
n=4 n=6
2Si 4Si 2e adz) 1+,r 1+,r 1+,2- 1+,2- 1 1

4Ge 6Ge (z z - i -i) bz(y) 3+,4- 3+,4- 3+,4- 1+,2- 1 1
C Zv b, (x) r,4+ 3-,4+ r,4+ 1-,2+ 1 1
Table 8.9. Phonon symmetry in (Si)m(Ge).[O 0 1] superlattices with space group Dl:
(m +n = 2k + 1)
m=1 m = 1 m =2 q fl r M X P N
n=2 n=4 n=3
2Si 2Si 2Ge 2a b2 (z) 2+,3- 1 2 2 1+,2-

(0 0 0) e(x,y) 5+,5- 3,4 1,2 1,2 1,2
D2d
4Si 4e a, (z) 1+,2+,3-,4- I, 1 1,2 1,2 1+,1+,2-,2-

4Ge 8Ge (z z 0) b2 (y) 5+,5- 3,4 1,2 1,2 1,2
4Ge
C Zv b,(x) 5+,5- 3,4 1,2 1,2 P,2
of 2.22 and 3.64 Arespectively [8.9, 10]. The superlattice period was repeated
100 times.
The superlattice normal modes may be characterized according to their
spatial distribution as the modes confined in the GaAs and AlAs layers (the
GaAs-like and AlAs-like optical phonons) and the modes propagating parallel
to the interface (the interface modes). In [8.9, 10] only the confined phonons
were observed since for the scattering geometries used the interface phonons are
forbidden. (They appear in the case of resonant excitation of vibrational and
electronic states when the k-conservation law for vibrations is lifted.)
The Raman measurements were performed in Brewster angle reflection
scattering geometries z(x'x')z and z(x' y')z from the (001) surface with 5145 and
1.0.,.----------~I~LO=-1----, Fig. 8.4. First order Raman scattering

spectra by LO, phonons (r1 for even / and
-If-- ~
:. r 2 for odd I) confined in GaAs layers of the
(GaAsb (AIAs)6 superlattice for z(x'y')z
xy L03 C
;: and z(x'x')z scattering configurations.
'C
0.5
x 1/4.5 LOs !
~ L02 T = 10 K. Ai = 5145 A[8.9]
:::l 1,1:
~
~
iii
c
Q)
~ 0
~:LO::1~~::J"\ \\~O, N T=~-I
xx L06 1 ;
0.5
r~ :
T02 IF;~
LOB I I j
/\. L0 10 I /,./.]
.... ~... M..
o ........ .
260 280 300
Raman shift [cm-1]
1.0 ...-----------"""'L"""'0,.....2---,-1----,
L04' f! L01 Fig. 8.5. First order Raman scattering

-if- ,'\ 'Ii spectra by LO, phonons (r1 for even I
TO
xx
I "i: \
l ,Ii \\
and r2 for odd /) confined in AlAs layers
of the (GaAsh(AlAs)18 superlattice for
.~ 0.5
'c" I I/ I \', z(x'y')z and z(x'x')z scattering configu-
Q) '\ ~ LO \ "~ rations. The arrow marks the position
~ xy ~ ~..p..::j 3 \.~:: of the LOo(F) phonon line with WLO =
~/~ LOa
405.8 cm- 1 for bulk AlAs. T = 10 K.
o~ - , Ai = 5145 A [8.10]
330 370 410
Raman shift [cm-1]
4880 Alines of an Ar+ -ion laser nonresonant with exciton transitions at low
temperatures (T = 10 K).
Figure 8.4 shows the first order Raman spectra of the (GaAs)21 (AIAs)6
superlattice in the region of confined GaAs LO l modes. The first order Raman
spectra of the (GaAsh(AIAs)18 superlattice obtained in the region of AIAs-
confined phonons are shown in Fig. 8.5. The Raman spectra measured in the
frequency region corresponding to second order scattering by confined phonons
in the (GaAsh1 (AIAs)6 superlattice are shown in Fig. 8.6.
These spectra can be interpreted by using the results of Sect. 8.3.1; the
observed lines are very narrow indicating the high quality of the superlattices.
For example, the measured linewidth (full width at half maximum) of GaAs-
confined LO l phonons is 1.50 0.05 cm- 1. For comparison, the linewidth of the
bulk GaAs LO-phonon line is 0.85 0.05 cm -1 [8.9, 10].
The symmetry of the (GaAsb (AIAs)6 and (GaAsh(AIAs)18 superlattices is
Did' The primitive cells contain 54 and 50 atoms and the number of normal
vibrational modes is 162 and 150, respectively.
Fig. 8.6. Second order Raman scattering

spectra of the (GaAsh I (AIAs)6 superlattice
for z(x'y')z and z(x'x')z scattering con-
figurations. T = 10 K. A. i = 5145 A[8.9]
O~--~-----T-----r----~--~
500 700 900
Raman shift [cm- 1]
From Table 8.2, the arrangement of atoms over the Wyckoff positions for
these superlattices is the following [the arrangement for the (GaAsh(AIAs)18
superlattice is given in parentheses]: one Ga atom is at the position 1a (000) with
site symmetry group 42m; one As atom is at the position Ie (0,1/2,1/4) - 42m;
20Ga (6Ga) and 6AI (18AI) atoms are in pairs at the positions 2e (OOz)(OOz)-mm
and 26As (24As) atoms are at the positions 2i (0,1/2, z)(1/2, 0, z)-mm.
The phonon symmetries of these superlattices are obtained in a manner
similar to those given in Table 8.4. Next, one can determine which groups of
atoms in the primitive cell contribute to the phonons of a given symmetry. For
example, the full mechanical rep at the r-point for the (GaAshl (AIAs)6 super-
lattice is
26rl(Ga~;AI~;Asf) + 28r2(Ga~.e;AI~;As~,J) + 54rs(Ga:;e;AI:Y;As~.Yf)

(8.3.9)
It is seen that only z-components of the displacements of the Ga and Al atoms

at e-positions as well as of the As atoms at i-positions contribute to r 1 modes.
For r2 modes there are also additional contributions from the Ga atom at the
a-position and from the As atom at the e-position. For rs modes there should
be contributions from the xy-displacements of all the atoms in the primitive cell.
Using the selection rules given in Sect. 8.3.1 the Raman spectra shown in
Figs. 8.4-6 can be interpreted. For the (GaAshl(AIAs)6 superlattice, the con-
fined LO l phonon line assignments together with their measured and calculated
frequencies are given in Table 8.10. The calculations are based on a two-atomic
linear chain model [8.9, 10]. The assignments of allowed phonons in the second
order Raman scattering spectra and their frequencies and given in Table 8.11.
In conclusion we would like to note that experimental study of first
8.4 Phonon Symmetry in High-Temperature Superconductors 227
Table 8.10. Assignments and frequencies [cm -I] of the observed GaAs-
confined phonons for the (GaAshl (AIAs)6 superlattice and values calculated
for the two-atomic linear chain model
Number of w LO, Number of wLO,

confinement confinement
and symmetry expt. calc. and symmetry expt. calc.
I (T2) 295.7 295.8 7 (T2) 288.5 288.4

2(Td 295.1 295.3 8 (Td 285.7 285.8
3 (T2) 294.4 294.4 9 (T2) 284.0 283.4
4 (TI ) 293.3 293.3 10(Td 281.6 281.6
5 (T2) 292.2 291.8 II (T2) 279.0 278.8
6(Td 290.6 290.1
Table 8.11. Assignments and frequences of the GaAs-confined phonons in

the second order Raman spectrum of the (GaAshl (AIAs)6 superlattice
Scattering geometry
x/x' x'y'
Phonon Frequency Phonon Frequency

combination [cm- I ] combination [cm- I ]
LO I + LO I [T2]2 591.4 LO I + L0 2 TI x T2 586.3

L0 2 + L0 2 [TI ]2 590.2 LO I + L0 4 TI x T2 582.4
L0 3 + L0 3 [T2F 588.8 L0 3 + L0 4 TI x T2 580.5
and second order Raman scattering in superlattices together with theoretical

analysis using induced reps of space groups can be employed as a sensitive and
precise tool to determine the atomic structure of superlattices.
8.4 Phonon Symmetry in High-Temperature Superconductors
There is considerable theoretical and experimental activity in the study of

phonons in single crystal high-temperature superconductors [8.13]. This is be-
cause the vibrational modes appear to be responsible for their superconductiv-
ity. In addition, the phonons are very sensitive to a change in the crystal micro-
structure. This opens up the possibility of investigating the behavior of specific
groups of atoms and their role in the superconductivity mechanism.
Among the high-temperature superconductors being studied there is a
family of single crystals [La 2Cu0 4, BizSrzCan-1Cun02n+4 (n = 1,2,3) and
Tl 2Ba zCa n_1Cu n O Zn + 4 (n = 1,2,3)] whose symmetry is specified by the same
space group Dl~ but whose crystal structures (i.e., the atomic arrangement over
the Wyckoff positions) are different.
Table 8.12. Phonon symmetry in high- 1'. superconductors with space group Dl: (l4/mmm) N
N
00
La 2Cu04 (TI/Bi)2(Ba/Sr)2Ca._t CU.0 2.+ 4 q P r M X P N

!'O
n = I n=2 n=3
Cu Cu - Cui la a 2.(z) r 3- r 3 2-
8:
(000) e.(x, y) 5- 5- r,4- 5 1-,2- [
D4h ~
]
- Ca - Ib a2.(z) r r r I 1+ r,:
5- 5- r,4- 1+,2+ ::s
(1 1 0) e.(x,y) 5
~
D4h 0'
::s
en
01 01 - 01 2c bt.(z) r,4- r,4- 3+,4+ 5 1+,2- o
-,
~
(1 0 1) b3.(x) 5- 5- 1+,2+ 3,4 2+,2- 'tl
D2h b2.(y) 5- 5- 1+,2+ 1,2 1+,1- @
C'l
m TI/Bi TljBi TljBi 2e at(z) 1+, r 1+,3- 1+,2- 1,3 1+,2- 8
La Ba/Sr Ba/Sr Ba/Sr (z z 0) e(x,y) 5+,5- 5+,5- 3,4 5, 5 1,2 .gen
02 02 03 C4v S'
03 03 04 ~
Cu Cu2 o
::s
Ca o
::s
~
- - 01 02 4g at (z) 1+,2+,r,4- 1+,2+,3-,4- 3,4 5, 5 1+,1+,2-,2-

(z + 1z 1) bt(x) 5+,5- 5+,5- t,2 1,2,3,4 1,2
a8en
(')
C2v b2(y) 5+,5- 5+,5- 1, 2 1,2,3,4 1,2 o
~
o
-,
..,(")
'<
en
a
en
Fig. 8.7. Crystal structure of La 2 Cu0 4 ; space group

D17
4h
.0
02(2e)
o Cu
Cu (1a)
01 (2c) ~La
As in the ca'se of superlattices, the use of the method of induced reps of space
groups is very effective since all the crystals belong to the same space group.
Thus, using the induced reps and the atomic arrangement data we can obtain
the phonon symmetry for each of the crystals in question.
The results of the analysis are presented in Table 8.12. The structure
data for the crystals are taken from [8.14] for La 2Cu0 4 [8.15] for
Bi 2Sr 2Ca n- 1 CU n 0 2n + 4 , and [8.16] for Tl2Ba2Can-l CUn 0 2n + 4 . The corre-
sponding atomic structures are shown in Fig. 8.7 for La 2Cu0 4 and in Fig. 8.8
for T1 2Ba 2Ca n- 1 CU n 0 2n + 4 .
It should be noted that the La2Cu04 crystal retains its tetragonal structure
at room temperature only when the high-temperature phase is stabilized by a
strontium or barium atom; the Bi 2Sr 2Can - 1 CUn02n+4 crystals are tetragonal
only in the zeroth order approximation since that structure has a long-wave-
length superstructure superimposed on it [8.17].
It can be seen from Table 8.12 that the phonon symmetry types in the
(TljBih(Ba/Sr)2Can_l CU n 0 2n + 4 (n = 2,3) crystals are the same although the
number of normal modes with a given symmetry and the types of atoms
which contribute to these modes depend on n. In the La 2Cu0 4 and
(TljBiMBa/Sr)2Cu06 crystals there are no phonons with symmetry r;, Mi,
and Xl.
The results given in Table 8.12 also show that in the (Tl/BiMBa/Sr)2
Ca n- 1 CU n 0 2n + 4 crystals with an even number of Cu-0 2 planes the vibrations of
the atoms of the central plane differ in symmetry from the vibrations of the
corresponding atoms of the other Cu-0 2 planes.
From the phonon symmetries of this table the selection rules for the first
and second order infrared and Raman spectra were derived; the complete data
set is found in [8.18, 19]. The second order optical spectra contain more
information about the crystal structure than the first order ones, as was already
mentioned in Sect. 8.3.1. For example, the second order Raman spectra of
(c) n=3
.x;'Zy
~
, o 1
0 i
,
~ o 0
~
bS~
o
:
0
:
04
4%r TI
03
~
TI
03 02
0
02 0 : 0 Cu2
01
0
o Cu
o
Cu
Ca ~ I
,
0 '0 0
,
01
Cu1
Ca
~
TI
Ba o 0
e Ca Ba 0
Ba
~o);07
.c= ,;;'-
~15~
~ \
Fig. S.Sa-c. Crystal structure of T12Ba2Ca.-1Cu.02.+4; space group D!~; (a) n = 1; (b) n = 2;
(c)n = 3
La 2Cu0 4 and Tl 2Ba 2Cu0 6 have the allowed phonon combinations [r4J 2,
r 4 x r 4 ; [M4"J 2, M4" x M4"; [P2J 2, P2 X P2; [XiJ2, and Xi x Xi which are
seen from Table 8.12 to involve the contributions only from 01 atoms.
Therefore, the lines in the second order Raman spectra corresponding to these
phonon combinations convey information only about the 01 sublattice. In
contrast, in the first order infrared and Raman spectra the vibrations with
symmetry r4- which convey information about the 01 sublattice are not
allowed.
The interpretation of Raman spectra of the bismuth superconductor family
Bi2Sr2Can-l CUn02n+4 can be considered as a good example of the application
of the symmetry analysis given in Table 8.12 in combination with a comparison
of the spectra of different bismuth compounds.
The most investigated compound from the bismuth superconductor family
is Bi 2Sr 2CaCu 20 s H (Bi-2212). The Raman spectra of the Bi-2212 compound
are presented in [8.20-25]. The spectra agree with each other rather well. The
spectra from [8.23J are shown in Fig. 8.9. However, the interpretations given by
different authors, disagree significantly. This is probably caused by the
Fig. 8.9. Raman spectra of Bil_.(Cal_ySry)x06 (x "" 0.22,

o (Cu) O(Sr) o (Bi) Y "" 0.53) crystals in the (zz) scattering geometry,
Bi B1g
I Bi 2Sr 2Cu0 6H (Bi-2201) ceramics and Bi2Sr2CaCu20S+6
Sr (Bi-2212) crystals in the (zz) and (xx) scattering geometries.
Cu (Cu T = 300 K [8.23]
A1g
Bi-Ca-Sr-O
zz
(2201 )
zz
(2212)
xx
800
Raman shift [cm 1]
complexity of the spectra due to the complex crystal structure with a large
number of atoms in the primitive cell.
To correctly identify the Raman spectra of the bismuth superconductors,
the results of the group theory analysis given in Table 8.12 could be used. In so
doing, one should bear in mind that, as was mentioned before, the majority of
bismuth superconductors have a superstructure with a periodic modulation of
the tetragonal structure (Dln in the direction of the square diagonal in the base
plane, lowering its symmetry to an orthorhombic structure. For the
orthorhombic Bi-2212 structure with the space group Dl~, the normal modes at
the F-point are given by (two formula units per primitive cell) [8.23]
r(Di~) = 12Ag + 7B1g + 14B2g + 9B3g + 8Au + 14B1u + 10B2u + 16B3u .

(8.4.1)
However, taking into account that in the orthorhombic Bi-2212 structure

the shifts of the atoms from their tetragonal positions are small, a
quasi-tetragonal approximation with the space group Dl~ can be used in many
cases. Then, using the results given in Table 8.12, the normal modes at the
F-point for the Bi-2212 crystal can be immediately written as
(8.4.2)
with the F/(A 19 ) mode being Raman-active in (xx), (yy), and (zz) scattering
geometries, Ft(B 19 ) in (xx) and (yy), and Fs+(Eg) in (xz) and (yz) geometries.
In the Raman spectra of the Bi-2212 compounds, the most intense lines
should be assigned to quasi-tetragonal normal modes since a small orthor-
hombic distortion can induce only weak spectral lines.
Additional information can be obtained from a comparison of the Raman

spectra of a group of bismuth compounds differing from each other by a struc-
ture element.
As mentioned, in Fig. 8.9 the Raman spectra of the Bil-X(Cal-ySry)xOo
(x ~ 0.22, y ~ 0.53), Bi 2Sr 2Cu0 6 H, and Bi2Sr2CaCu20sH compounds are
presented. [All the samples were grown by A.A. Bush (Institute of Radiotechnics,
Electronics Automatics, Moscow)]. The Bil-ACa1-ySry)xOo crystal is com-
posed of alternating Bi-O and Bi-Ca-O (or Bi-Sr-O) layers stacked along the
z-axis [8.26, 27J and resembles the structure of bismuth superconductors. Note
that the frequencies of the most intense Raman lines of this species, at approxi-
mately 43, 83, and 660 cm -1, show a weak dependence on the concentration of
Ca and Sr atoms. In addition, according to group theory analysis [8.28] (with
the space group R3m [8.27J being analyzed) the normal modes involving the
vibrations of these atoms are forbidden in first order Raman scattering. There-
fore, the Raman-active modes at 43 and 83 cm -1 can be attributed to bismuth
vibrations whereas the mode at ~ 660 cm -1 can be assigned to the vibrations of
oxygen atoms in the Bi-O planes.
In the quasi-tetragonal approximation, the normal modes of the
Bi 2Sr 2Cu0 6 (Bi-2201) crystal at the r-point can be written as (Table 8.12)
(8.4.3)
with the rt(A 19 ) mode being Raman-active in the (xx), (yy), and (zz) scattering
geometries, and rs+(Eg) in the (xz) and (yz) geometries.
It is well known that the strongest Raman lines of the high- I;, supercon-
ductor, including the bismuth ones, correspond to phonons with the symmetry
of the identity rep.
As can be seen from Table 8.12, the A 1g modes involve the vibrations of Bi
and Sr atoms as well as 02 and 03 oxygen atoms in the Sr-O and Bi-O planes.
As for the Bil-ACal-ySry)xOo compound, the A 1g mode at 80 cm- 1 can be
assigned to bismuth vibrations whereas the A 1g mode at 629 cm- 1 is attribut-
able to the vibrations of the 03 oxygen atoms in the Bi-O plane. In comparison
with the Bil_ACa1_ySry)xOo crystal, an additional low-frequency line at
118 cm- 1 appears. This may be assigned to the A 19 mode involving the vibra-
tions of the Sr atoms.
Since a fairly strong line near ~461 cm- 1 is observed for all the bismuth
superconductors it can be assigned to the A 19 modes involving the vibrations of
the 02 oxygen atoms in the Sr-O planes.
As can also be seen from Table 8.12, for the Bi-2212 compound, the A 19
modes involve the in-phase vibrations of Bi, Sr, and Cu atoms as well as the
in-phase vibrations of 01,02, and 03 oxygen atoms lying in the Cu-0 2, Sr-O,
and Bi-O planes. On the other hand, the B 19 mode involves the out-of-phase
vibrations of the 01 oxygen atoms in the CU-02 planes. Analyzing the addi-
tional lines appearing in the Raman spectra of the Bi-2212 crystal which are
absent from the spectra of the Bi-2201 compound and using the corresponding
8.5 Phonon Symmetry in Diperiodic Systems 233
selection rules for different scattering geometries one can obtain the following
interpretation of the Raman spectra of the Bi-2212 compound.
The A lg modes involving the heavy atom vibrations are at 62 cm-l(Bi),
118 cm-l(Sr), 148 cm-l(Cu) whereas the modes involving the oxygen vibrations
are at 296 cm- l (B lg mode; oxygen in CU-02 plane), 395 cm-1(A 1g ; Cu-0 2),
456 cm-1(A lg ; Sr-O), and 626 cm-1(A 1g ; Bi-O) [8.23]. Thus using group theory
analysis one can assign all the strong Raman spectral lines for the family of
bismuth superconductors.
In summary, it should be noted that new techniques allow one to fabricate
complex crystal systems with varying primitive cell parameters. Thus, the meth-
od of induced reps of space groups is very promising in applications to lattice
dynamics since it allows the possibility of determining the phonon symmetry for
an entire single crystal family having the same space group and of analyzing the
variation of the phonon spectra within the family.
8.5 Phonon Symmetry in Diperiodic Systems

The method of induced reps of space groups has also proved to be very effective
in determining the vibrational properties of diperiodic systems which are weak-
bounded subsystems of three-dimensional crystals. As an example we consider
the crystal family of high-r:, superconductors TI2Ba2Can-lCun02n+4 already
discussed in Sect. 8.4.
Since the number of atoms in the primitive cell in these systems is very large,
the assignment of spectral lines is rather complicated. However, it is possible to
obtain additional information about the lattice dynamics simply from symmetry
considerations if we take into account that the crystals have a pronounced layer
structure. In these crystals, the atoms within the layers are bound by covalent
forces whereas the interlayer interactions are determined predominantly by the
van der Waals forces.
Since in high-r:, superconductivity the Cu-0 2 layers play the main role
[8.29, 30] we consider first an isolated Cu-0 2 layer and then include the inter-
layer interaction as a perturbation. In this approximation a number of bulk
normal modes originates from the intralayer Cu-0 2 normal modes. In some
cases, this leads to a small Davydov splitting of the spectral lines that helps to

identify the corresponding lines in the bulk spectra originating from the vibra-
tions of Cu and atoms in the layer. This information, based only on symmetry
considerations, simplifies significantly the assignment of the lines. The interlayer
interaction could also modify the optical selection rules. The phonon combina-
tions being inactive in the single layer approximation become active in the
transformation to the bulk mode combinations. The weakness of the corre-
sponding lines in second order infrared and Raman spectra helps to identify
them in the spectra.
This single layer approach was first proposed in [8.31] for the analysis of
infrared and Raman spectra of AS 2S3 and AS 2Se 3 layered crystals and used later
Fig. 8.10. Crystal structure of the L3 isolated layers of

T1 2 Ba 2 Can _ 1 CUn 0 2n + 4
01 (2c)
Cu (1a)
I
);IZ
I I
1I 1I o Cu
I I : 0
:x I
I
yl
I
I
in [8.32] for the optical spectra of TISbS 2 . However, the authors restricted
themselves to only the k = 0 case.
It has been found that there are three types of Cu-0 2 layers in
T1 2 Ba 2 Can - 1 CUn 0 2n + 4 compounds [8.33]. For n = 1, there exists one layer (L1)
with symmetry described by the diperiodic group DG61 (P4/mmm). For n ~ 2
there appears two layers (L3) with symmetry P4mm (DG55), and for n ~ 3 these
two layers are accompanied by (n - 2) layers (L2) with symmetry P4/mmm
(DG61) but differing from L1 in the atomic arrangement over the Wyckoff posi-
tions.
As an example, we consider the L3 layers with the crystal structure shown
in Fig. 8.10. The layer space group P4mm (DG55) is a subgroup of the corre-
sponding Fedorov group G = cl v ' Simple induced reps of a diperiodic group
DG can be obtained from simple induced representations of a corresponding
Fedorov group G (Sect. 6.2.2). Writing the space group Gas
g = (R;lv; + a.) E DG (8.5.1)
one should choose from the table of the induced reps of G only those lines and
columns which correspond to q E QVG and k E KVG (wave vectors lying in the
Brillouin zone of the layer are shown in Fig. 8.11), Sect. 6.2.3.
The phonon symmetry for an isolated Cu-0 2 layer (L3) for the symmetry
points of the square 2D Brillouin zone is given in Table 8.13 together with the

arrangements of Cu and atoms over the Wyckoff positions in the layer group
(the layer atom labeling corresponds to that in the bulk). The labels of the irreps
of the layer group correspond to those of the related Fedorov group.
We now establish by symmetry the correspondence between layer (Table
8.13) and bulk (Table 8.12) normal modes. In this case, the layer group DG is a
subgroup of the Fedorov group G of the bulk crystal. Therefore, to determine
the symmetry of the bulk modes originating from a layer mode, the rep I(D) of
the group G induced by the irrep D of the layer subgroup DG should be decom-
posed into irreps of G. Since the layer kl and bulk kv wave vectors satisfy the
condition
(8.5.2)
8.5 Phonon Symmetry in Diperiodic Systems 235
z Fig. 8.11. Brillouin zones of TI 2 Ba 2 Ca n _\ CU n 0 2n +4
)- bulk crystals (a) and the L3 isolated layer (b)

ky
kx
(a)
r X
~
"lc======~M (X)
(b)
Table 8.13. Phonon symmetry in Cu-0 2 layers (L3) with space

group P4mm (DG 55)
n=2 n=3 q p r M X
(0 0) (H) (0 1)
C4v C4v C 2v
Cu Cu2 la a\(z) 1 1 1
02 03 (0 0 z) e(x,y) 5 5 3,4
C4v
01 02 2c a\(z) 1,2 5 1,3

(0 1 z) b2 (y) 5 1,2 1,4
C 2v b\(x) 5 3,4 2,3
where hi is a layer reciprocal lattice vector, the irreps of G belonging to different

stars of the wave vector may appear in the decomposition.
Thus, the symmetry of the bulk modes corresponding to layer modes in r
and M points of the Brillouin zone of the layer may be determined. In the
present case, the layer modes with kl = r induce the bulk modes with kv = r
and kv = M, whereas the layer modes with kl = M induce the bulk modes with
kv = X. For particular normal modes we have
(8.5.3)
(8.5.4)
(8.5.5)
M1,3 -t 2(X;- + Xl) (8.5.6)
M 2 ,4 - t 2(Xl + xn (8.5.7)
From the above relations it follows that the frequencies of the bulk modes
with symmetries rt and r 3- (as well as r/ and r4-, r/ and r 5-) originating
from the corresponding layer modes should be very close. Since the layer group
has no inversion the layer modes r 1 annd rs are both infrared- and Raman-
active. In contrast, the symmetry group of the bulk crystal contains an inversion
and in the corresponding Davydov doublets originating from the layer modes
the even components rt and rs+ are Raman-active whereas the odd compo-
nents r 3- and r s- are infrared-active. These doublets in the bulk crystal spectra
responsible for the intralayer vibrations can be easily detected. The splitting is a
measure of the interlayer interaction.
From the above relations the proximity of the frequencies of normal modes
at r- and M -points of the bulk Brillouin zone also follows. Hence, the bulk
modes originating from the layer modes are nearly dispersionless in the r - M
direction.
The interlayer interaction also modifies the selection rules obtained for the
single layer model. For example, the infrared- and Raman-inactive layer over-
tone [Ml]2 induces the bulk mode overtones [Xt]2 and [Xi:? which are
Raman-active in (xx), (yy), (zz), and (xy) scattering geometries and an xi x Xi:
combination which is infrared-active in z-polarization. However, the corre-
sponding lines in the second order bulk spectra will be vanishingly weak and
can be hardly observed. The exclusion of these lines simplifies the interpretation
of the second order spectra.
The layer approach to the analysis of phonon symmetries in high-tempera-
ture superconductors has further been developed in [8.34 - 38]. The quasi-two-
dimensional nature of phonon subsystems in perovskite-like-superconductors
was established. It has been shown that the normal modes of layer crystals can
be divided into 3 acoustic and 3 (NL - 1) interlayer optical and 3 (NA - N L ) in-
tralayer optical modes where NL and NA are the numbers of layers and atoms
per primitive cell, respectively. The interlayer bulk modes originate from
acoustic layer modes whereas the intralayer bulk modes are induced by optical
modes of isolated layers.
The results of these studies were summarized in [8.39, 40]. The Raman
spectra of high-temperature superconductors were discussed in detail in [8.39].
The comprehensive group-theoretical analysis of layer and bulk normal modes
supplemented by the results of lattice dynamical calculations was given in
[8.40].
A similar approach has been used for the analysis of vibrational spectra
of fullerenes C60 and C70 where the normal modes of bulk molecular crystals
have been divided into intramolecular and intermolecular modes [8.41, 42].
9. Site Symmetry in Magnetic Crystals
and Induced Corepresentations
We briefly consider the method of site symmetry in magnetic crystals and its use in the theory of
induced co-representations. Some applications of this theory are discussed.
9.1 Shubnikov Space Groups of Symmetry of Magnetic Crystals
Shubnikov space groups S contain the operation of anti symmetry ao that re-
verses a magnetic moment of atoms in a magnetic crystal. Depending on the
way of combining of space group operations (Rlv) with the operation of anti-
symmetry ao (a6 = E) Shubnikov space groups are subdivided into four types.
Type I are the 230 Fedorov space groups G. A type II Shubnikov space group
S is given by SII = G + aoG and is called a "gray" space group, of which there
are also 230. In a paramagnetic phase all crystals belong to a gray space group
because the anti unitary operation a o is the operation of time inversion. A type
III Shubnikov space group is given by SIll = H + ao(G - H) where H is a
halving unitary subgroup of the Fedorov space group G and (G - H) contains
no pure translations, i.e., SIll groups are based on ordinary Bravais lattices. As
a halving subgroup, H may be chosen in one of several ways for any given
Fedorov group G. Therefore the total number of SIlI black and white space
groups is 674. Type IV black and white Shubnikov space groups contain
a translation to of one of 22 black and white Bravais lattices: SIV = G +
ao{Elto}G. There are 517 type IV Shubnikov groups. All 1651 Shubnikov space
groups are listed in [9.1].
As an example we consider all Shubnikov groups generated by the Fedorov
group Dl:(P4 2/mnm). As a type I Shubnikov group, this Fedorov group is
number 495 on the list of 1651 Shubnikov groups. Primes indicate those spatial
operations of the Fedorov group which are multiplied by the operation ao
which commutes with all the elements of Fedorov groups. The gray group of SII
type is denoted by P42/mnm1' (496). There are seven SIll-type groups corre-
sponding to a simple tetragonal uncolored Bravais lattice: P42/m'nm (497),
P4~/mn'm (498), P4~/mnm' (499), P4~/m'n'm (500), P42/mn'm' (501), P4~/m'nm'
(502), P42/m'n'm' (503). From an uncolored simple tetragonal Bravais lattice
with primitive translations ai' a 2, a 3 three black and white Bravais lattices are
derived: Pc (to = 1I2a3), Pc [to = 112(al +a2)], PI [to = 112 (al +a2 +a3)]'
One thus obtains three SIV_ type Shubnikov groups: Pc42/mnm (504),
PC42/mnm (505), P I 4 2/mnm (506).

238 9. Site Symmetry in Magnetic Crystals and Induced Corepresentations
There are several alternatives to using an adaptation of the international

space-group labels. For type III Shubnikov space groups the Schonflies nota-
tion in the form G/H may be used so that, for example, P4~/mnm' would be
written as Dl:/DJ~. Koptsik [9.2] uses a label for any type of Shubnikov space
group of the form IIl~ where x is the number (from 1 to 230) of the related
Fedorov space group and y is the number given to that Shubnikov space group.
In this notation, for example, P4~/mnm' would be IIli~~.
The classification of Shubnikov point groups M is made using the same
principles as for space groups: type I-the ordinary (crystallographic) point
group F(32), type II-the gray point groups MIl = F + aoF (32), type III-the
black and white (or magnetic) point groups MIll = H + ao (F - H), where H is
a halving unitary subgroup of point group F(58). As an example, we consider all
type III magnetic point groups which are derived from the C4v (4mm) point
group with symmetry operations E, ctz, C 2z , (Jx, (Jy' (Jxy, (Jxy' This derivation
may be made by studying the one-dimensional reps of C4v (Table 3.6). If the
identity irrep of C4v is regarded as synonymous with the type I Shubnikov
group C4v then the remaining three real one-dimensional irreps of C4v can be
related to the type III Shubnikov groups M that are derived from the C4v group
irreps in Table 3.6 [9.1]. In irrep a 2 of C4v the elements E, C2z , ctz are
represented by + 1, while (Jx, (Jy, (Jxy, (Jxy are represented by -1 and become
colored in M. Thus the type III group 4m'm' is derived (the primes indicate the
elements associated with a o). In a similar way the irrep bi corresponds to the
type III point group 4'mm' and the irrep b2 to the group 4'm'm. However, type
III magnetic groups 4'mm' and 4'm'm are not really different as they are related
by a 45 rotation about the z-axis.
The paramagnetic crystals (in which the magnetic moments of atoms are
randomly oriented) are described by the gray Shubnikov space groups SII. The
ferromagnetic crystals (all magnetic moments are parallel) may belong to a
non-colored (Fedorov) space group G = Sl or to a type III Shubnikov space
group SIll. The antiferromagnetic crystals (all magnetic moments are either
parallel or anti parallel and arranged so that there is no net magnetic moment)
may belong to Shubnikov space groups Sl, SIll, or SlY.
In the next section we consider the crystal structures of magnetic crystals
belonging to Shubnikov space groups of different types.
9.2 Site Symmetry in Magnetic Crystals
When defining the site symmetry group Sf of an atom in a magnetic crystal it

should be borne in mind that the symmetry operations of the magnetic group
act simultaneously on the space coordinates of the atom and on its magnetic
moment, which transforms as an axial vector. In general, the site symmetry
group Sf may be found as follows [9.3]. In the initial magnetic group one
should replace the antiunitary operations with corresponding unitary ones by
excluding the operation a o of the reversal of the magnetic moment. Thus one
obtains some Fedorov space group G (which is said to be re-isomorphic with the
9.2 Site Symmetry in Magnetic Crystals 239
initial magnetic group) and the site symmetry group Gf ofthe given atom can be
easily found. By restoring the operation ao one gets the desired site symmetry
group Sf'
Diamagnetic and paramagnetic crystals are described by the gray space
groups SII = G + aoG; the site symmetry groups are also gray: Sf = Gf + aOG f .
Let some crystal be paramagnetic above the Neel temperature TN (the
magnetic moments of the atoms are randomly arranged) and antiferromagnetic
below TN (the magnetic moments are parallel or antiparallel). As the crystal
passes from the paramagnetic phase to the antiferromagnetic phase there are
two possibilities: 1) the basis vectors of the Bravais lattice are the same in both
phases (the magnetic ordering does not change the size of the primitive unit cell);
2) in the magnetically ordered phase the unit cell size increases.
As an example of the first kind let us consider the MnF2 crystal with rutile
structure in its paramagnetic phase [space group Dlt- P4 2/mnm, aD2h(Mn),
jC2v (F)]. In the antiferromagnetic phase the magnetic moments of Mn atoms in
the same primitive unit cell are antiparallel and oriented along the z-axis. To
find the symmetry of the magnetically ordered phase one takes into account that
spatial inversion 1 does not change the axial vector of the magnetic moment.
Therefore the coset representatives (EIO), (C2z IO), (110), (crzIO) of the decomposi-
tion (3.4.1) are not accompanied by the antiunitary operation ao of the reversal
of the magnetic moment. The operations (UxIH!), (UyIH!), (crxIH!), (cryIH!) are
also the symmetry operations of the magnetic phase, as their rotation compo-
nents Ux , Uy change the sign of the z-coordinate and the translational part
transforms the first Mn atom to the second one of the same unit cell. The other
eight coset representatives in decomposition (3.4.1) (UxyIOOO), (UxyIOOO), (crxyIOOO),
(crXy 1000), (C,tzIH!), (s.rzIH!) are accompanied in the magnetic group by the
operation ao. Thus the Shubnikov group of the magnetically ordered phase of
.
M n F 2 IS SIll = D12
2h 2h or p4~
+ ao(Uxy 1000)D12 - -21 -2' = P4'2 / mnm ' .
m n m'
Consider the site symmetry change in the process of magnetic ordering. In
Table 9.1 the Wyckoff positions and their site symmetry groups are given in
Table 9.1. Wyckoff positions in the Fedorov D~:

and Shubnikov Dl: IDlf space groups
D14
4h D~:IDlf
2a m.mm m.m'm'
2b m.mm m.m'm'
4c 21m .. 21m ..
4d 4.. 4' ..
4e 2.mm 2.m'm'
4f m.2m m.2'm'
4g m.2m m.2'm'
8h 2.. 2..
8i m .. m ..
8j .. m .. m'
16k
Fedorov Dlt and Shubnikov Dlt/D~7. space groups. As the unit cell size is
the same for both groups the multiplicities of Wyckoff positions are also the
same. It is seen from Table 9.1 that in a magnetic crystal the site symmetry
groups may be both unitary (positions c, h, i, k) and magnetic point groups
(positions a, b, d - g, j).
In UO z crystals, transition to the antiferromagnetic phase is accompanied
by an increase in the unit cell. In the paramagnetic phase this crystal, with
fluorite-type structure, belongs to the gray Shubnikov space group SII = O~ +
aoO~; U 4 + ions occupy a-Wyckoff positions lying on the points of a face-
centered cubic (fcc) Bravais lattice. In the antiferromagnetic phase the magnetic
moments of the U 4 + ions within each horizontal sheet are all parallel; in succes-
sive sheets the magnetic moments are reversed. As a result, the third translation
vector a; in the antiferromagnetic phase is equal to twice a 3 (the third transla-
tion vector of the fcc lattice in the paramagnetic phase) and the volume of the
unit cell is increased by a factor of 2 in the magnetically ordered phase. The
latter belongs to the type IV Shubnikov group PA/mmm = Dlh + ao(Elto)Dlh
where to = t(a 1 + az + a;) with a tetragonal magnetic lattice. This Shubnikov
group is also labeled as mBg = Dl~/Dlh' In Table 9.2 the site symmetry groups
of Wyckoff positions are given for the Fedorov space group I4/mmm = Dl~ and
Shubnikov space group PA/mmm. The U 4 + ions occupy Wyckoff position a, the
oxygen atoms are at Wyckoff position c, so that the "magnetic" unit cell consists
of two UO z formula units.
The chalcopyrite crystal CuFeS z in the antiferromagnetic phase is described
by a type I Shubnikov space group (i.e., the usual Fedorov group). In the para-
magnetic phase the symmetry of this crystal is described by the gray Shubnikov
Table 9.2. Wyckoff positions in the Fedorov Dl; and

Shubnikov Dl; /Dlh space groups. For Fedorov space
group Dl; the multiplicites of Wyckoff positions
correspond to the crystallographic (tetragonal) unit cell
of a body-centered tetragonal lattice
D17
4h Dl;/Dlh
2a 4/mmm 4/mmm
2b 4/mmm 4/mmm
4c mmm. mmm.
4d 4m2 4'm2'
4e 4mm 4mm
8f .. 2/m 2'/m
8g 2mm. 2mm.
8h m.2m m.2m
8i m2m. m2m.
8j m2m. m2m.
16k .. 2 .. 2'
161 m .. m ..
16m .. m .. m
16n . m. . m.
320
9.3 Corepresentations of Shubnikov Space Groups 241
Table 9.3. Site symmetry groups of Wyckoff

positions in the Fedorov space group DU - 142d.
The coordinates of Wyckoff positions are given in
terms of the translation vectors of a bct lattice
q G. XYZ
2a 4.. ()()()
2b 4.. 0,0,1-
4c 2.. OOz
4d .2. x, 1/4, 1/8
8e
group Sll = Dii + aoDiJ. Let the origin of the coordinate system be chosen to
be at the Wyckoff position a with the site symmetry group Ga = S4' The coset
representatives of Dii in a decomposition relative to T [the translation group of
the body-centered tetragonal (bct) Bravais latticeJ are taken as
(EIO), (C2z IO), (S.izIO), (SizIO) ,
(C2x lv), (C 2y lv), (CTxylv), (CTxylv) ,
v = (3/4, 1/4, 1/2) . (9.2.1)
The improper translation v is given in units of the primitive translation vectors

of the bct lattice. The site symmetry of Wyckoff positions for the space group
Dii is given in Table 9.3. Two Cu atoms, two Fe atoms and four S atoms occupy
Wyckoff positions a, band d, respectively. Thus there are two formula units
CuFeS 2 per primitive unit cell.
In the antiferromagnetic phase the magnetic moments of two Fe atoms in
the unit cell are oriented along the z-axis, one of them is parallel and the other
anti parallel to that direction. The symmetry operations of the site symmetry
group 4(S4) of the Fe atom do not change the direction of its magnetic moment.
The remaining four operations in (9.2.1) transfer the first Fe atom into the
second one (since they contain the improper translation) and reverse the direc-
tion of its magnetic moment. Consequently, the CuFeS 2 crystal in the anti-
ferromagnetic phase is described by the unitary (Fed oro v) space group DiJ.
Note that in [9.4J it is erroneously stated that the CuFeS 2 crystal belongs to the
space group SJ.
A complete list of site symmetry groups for each of the type III and type IV
Shubnikov groups is given by Koptsik [9.2J and is illustrated with two-color
diagrams.
9.3 Corepresentations of Shubnikov Space Groups

The theory of co reps of magnetic point and space groups is an extension of the
representation theory to groups which contain anti unitary operators a. The
basic theory of coreps may be found in [9.1, 5, 6]. The main results of this
theory are summarized in this section. We write the magnetic group S as
G + ao G where the elements of G are unitary. All of the antiunitary operators
a may be obtained as the product of some anti unitary operator ao with suc-
cessive elements g of the unitary subgroup which is an invariant subgroup of
S. The multiplication law for the matrices of a corep DD is the following:
DD(g)DD(g') = DD(gg') , DD(a)DD(g)* = DD(ag) ,

(9.3.1)
DD(g)DD(a) = DD(ga) , DD(a)DD(a')* = DD(aa') .
The irreducible coreps of the group S are constructed from the irreps of the
invariant unitary subgroup G. Let D(g) be an irrep of G and ao be one of the
anti unitary operators. All of the anti unitary operators are of the form a = aog
where g ranges over all ofthe unitary operators of the group. The relation (9.3.1)
is satisfied by matrices of the corep
0 ) 0 D(aa o))
DD(g) =
( D(g)
0 D*(ao 1gao) , DD(a) = ( D*(ao1a) 0 . (9.3.2)
If the irreps D(g) and D*(a(/gao) are equivalent then there are two possible
cases depending on the matrix 13 in the equivalency relation D*(a o1 gao) =
p-1 D(g)f3.
In the first case 1313* = D(a6) and just one irrep D(g) is contained in the
co rep:
DD(g) = D(g) , DD(a) = D(aao 1 )f3 . (9.3.3)
Relation (9.3.3) means that the degeneracies of D(g) and DD coincide. The corep
is called to be of type a) in this case.
In corep of type b) 1313* = - D(a6) and one irrep D(g) of the unitary sub-
group is contained twice in the corep:
D(g)
DD(g) = ( 0
0)
D(g) , DD(a) = ( ( 0_ 1 13
D aao )
- D(aao 1 )13)
o . (9.3.4)
If the irreps D(g) and D*(a o1 gao) are inequivalent, the corep (9.3.2) is related
to type c), and the degeneracy of corep DD is twice that of D(g).
It can be seen from (9.3.2-4) that starting. with a rep D(g) of the unitary
subgroup G it is possible to determine an irreducible corep DD of S = G + aoG.
It is important to know which of three types a), b), c) is appropriate for a given
irrep of G. It has been shown that
(9.3.5)
where X is the character of D(g) [9.1].

9.3 Corepresentations of Shubnikov Space Groups 243
All the possible types of coreps of magnetic space groups are given in [9.1,
7] for the gray groups, in [9.5] for black and white space groups based on or-
dinary Bravais lattices, and in [9.6] for all types of magnetic space groups.
To illustrate the labels used for the coreps notation consider coreps of the
space group P421mnm' = D!t1D11 of the MnF2 crystal anti ferromagnetic
phase (Sect. 9.2). The irreps of the unitary subgroup D11 = Pnnm are charac-
terized by wave vector k from the Brillouin zone of the primitive orthorhombic
Bravais lattice. First it is necessary to establish the relationship between the
points and lines of symmetry in Brillouin zones for simple tetragonal (space
group P421mnm') and simple orthorhombic (space group Pnnm) Bravais lat-
tices. This relationship is given in Table 9.4 for the symmetry points [9.1]. The
point groups of wave vectors R and X (little cogroups) do not contain anti-
unitary elements so that coreps of the magnetic space group D!t I D11 for
these points coincide with irreps of the unitary space group D!t. Using the
characters of irreps of the unitary subgroup D11 for the symmetry points r,
S, Z, R one may use (9.3.5) to find the type a), b) or c) of the coreps. In the
last two rows of Table 9.5 the coreps labels of the magnetic space group
D!t1Di1 for the r-point of the Brillouin zone used in [9.1] and [9.6] are
given. In the first row of this table are the labels of irreps of the unitary sub-
group D11 (which are the same in [9.1] and [9.6]); in the second row the
type of these irreps is shown. The notation from [9.1] is more informative as
it shows the origin of a corep of a magnetic group from those of the unitary
subgroup, In this notation the coreps are denoted by the symbol D followed
by the k-vector label and numerical indices of those irreps of the unitary
subgroup which are contained in the corep. For example, Dri is the a)
type corep obtained from the real irrep ri of the unitary subgroup. Symbols
Table 9.4. The symmetry points

in Brillouin zones for Pnnm
and P4~/mnm'
P4~/mnm' Pnnm
T(O 0)
M(!,!,O)
T(O
s(!,!,o)
0)
Z(O,O,!) Z(O,0, !)
A(!,!, !) R(!,!,!)
R(O,!,!) U(!,Oj)
X(O, !,O) X(!, 0, 0)
Table 9.5. The coreps of the magnetic space group Dl: /Dlf for the r-point of the Brillouin zone
D12
2h ,
r,+ r+
2 r3+ r+
4
r,+
S r-, r-2 r-3 r4 r,-
S
Type a) a) c) a) a) a) c) a)
Corep Dr,+ Dr/ Dr3~4 Drs+ Dr,- Dr2- Dr3~4 Drs- [9.1]
labels Dr, Dr2 Drs Dr7 Dr3 Dr4 Dr6 Drs [9.6]
Dr3~4' Dr3~4 denote the c) type co reps for complex conjugated irreps r/, r/ or
r 3-, r 4- of the unitary subgroup. For b) type coreps (which are absent in this
example) the symbol DIi,i is used; irreps Ii and Ii* are equivalent.
For the space group PI 4/mmm with a tetragonal magnetic lattice the labels
of the coreps are connected with the Brillouin zone of the simple tetragonal
lattice since the unitary subgroup DJh = P4/mmm has this Brillouin zone. The
types of the irreps of the unitary subgroup DJh are analyzed using (9.3.5) and the
labels of the corresponding co reps may be introduced in the same manner as
was done for the space group DJ:/Di~.
9.4 Induced Corepresentations of Magnetic Space Groups
The extension of the theory of induced reps of unitary (Fedorov) space groups
to magnetic (Shubnikov) space groups turns out to be useful in defining the
symmetry of magnons (spin waves) in a magnetic crystal, in analyzing the sym-
metry of phonons in magnetic crystals and the magnon-phonon hybridization
as well as in finding the symmetry change in magnetic phase transitions. This
extension requires the use of induced coreps. Induced coreps were applied in
[9.8] to take into account the reality of displacements in lattice vibrational
problems.
The generation of induced co reps for Shubnikov space groups of different
types was considered in [9.3]. Just as an ordinary induced rep is a reducible rep
of a Fedorov space group, an induced corep is a reducible corep of the magnetic
(Shubnikov) space group induced by the corep of the site symmetry subgroup of
the magnetic group. To generate an induced corep it is enough to generate the
induced rep of the unitary subgroup of a magnetic group using the methods
considered in Sect. 4.2.
Induced co rep generation for the gray magnetic groups SI1 = G + aoG of
the symmetry of diamagnetic and paramagnetic crystals is based on the fact that
the site symmetry groups are also gray: Sf = Gf + aOGf In order to generate
the induced corep of the group SI1 induced by the site symmetry group Sf coreps
it is first necessary to generate the simple induced rep of the unitary subgroup G
for all qEQ. The irreps of the site symmetry unitary subgroups G q may be-
long to one of three types generating co reps of Sq of the same dimension for
type (a) and of twice the dimension for types (b) and (c).
If the irrep of the site symmetry group Gf belongs to type (a), the induced
rep of G is an induced corep of S. However, in the induced corep table it is
necessary to join the symbols of those irreps of group G which belong to types
(c) or (b) in a single symbol of the corep of the magnetic group S.
As an example we consider single-valued irreps of the gray magnetic group
P42/mnml' = Dl: + aoDl:. The simple induced reps of the unitary subgroup
Dl: are given in Table 4.5. For the Wyckoff positions a, b, c all the irreps of
unitary site symmetry subgroups belong to type (a), so that the corresponding
9.4 Induced Corepresentations of Magnetic Space Groups 245
rows of the induced rep table may be repeated in the induced corep table.
However, at the M point of the Brillouin zone there are pairs of complex conju-
gate irreps (1+,4+), (1-,4-), (3+,4+), (r,4-) of group Dl: belonging to type
(c). Their symbols have to be grouped in pairs in the induced corep table:
DM(1 +,4+), DM(1- ,4-), DM(3+,4+), DM(r ,4-).
If the irrep of the site symmetry group Gf belongs to types (b) or (c) then the
symbol of the induced rep of the group G must be obtained by doubling in case
(b) or joining in case (c) of symbols of the corresponding induced rep in the
k-basis. Further joining may be necessary if the irreducible components of the
induced rep obtained belong to types (b) or (c).
In dealing with black and white space groups one may encounter two cases:
the site symmetry group is unitary: Sq = Gq; the site symmetry group is black
and white: Sf = Gf + aOGf . In the first case induced coreps are generated as
follows. By inducing from the irreps of the group SIJ = GIJ on the unitary sub-
group G of the Shubnikov space group S one obtains the induced rep of the
group G in k-basis. Analyzing the characters of the irreducible components of
the induced rep obtained one establishes the types of the corresponding coreps
of group S in the following way.
One can write S as a sum of left co sets with respect to the site symmetry
group Sf = GIJ:
S= G + aoG = L (g"jG f + aog"Pf) ,

"j
(9.4.1 )
The q-point orbit with respect to the group S consists of two orbits with respect
to the unitary subgroup G: g"jq = qj + a" and aog"jq = q; + a". These two
orbits are generated by the points q and q' = aoq with site symmetry groups
Gf and Gf , = aOGfa(/. On subducing the induced corep (q,l') of the magnetic
group S to the unitary subgroup G one obtains two induced reps (q,l') and
(q',I') with basis functions W;Y)(r - all) = D(gllj) W;y)(r) and V;JY)(r - all) =
aoW;JY)(r - all)' The anti unitary operator ao transforms these two linearly inde-
pendent bases through each other. Therefore no irreducible component of the
induced corep (q,l') belongs to type (a). As a result, each full irreducible co rep
appearing in the induced corep (q,l') splits into two full irreps when subducing
on unitary subgroup G. One of these two irreps enters in the induced rep (q, y),
the second enters in the induced rep (q', y). Thus each small irrep of G appear-
ing in the induced rep (q, y) corresponds to a small irreducible corep [of type
(b) or (c)] in an induced corep of S.
To generate an induced corep for the black and white site symmetry group
Sf = Gf + aOGf one has to follow a four-step process. (1) Define the types of
co reps, (a), (b) or (c), of the site symmetry group Sf' (2) Subduce these coreps on
the unitary subgroup Gf . (3) Generate the induced rep of the unitary subgroup
G by induction from the subduced coreps. Let iX, p, a(u), a'(u) = a*(aij1ua o)
denote the irreps of GIJ and Dr", DI/" Dr" be the irreducible co reps of Sf for
Table 9.6a, b. Simple induced representations of the space group

D~~ - Pnnm and simple induced corepresentations of the magnetic
space group P4~/mnm' = D~~ + ao(UxyIOOO)D~~
(a) Simple induced representations of the D~~ space group
r S Z R X U
a b
a ag 1+2+ 3+4+ 1 1 1 1+ 1-
au 1-2- 3-4- 1 1 2 1- 1+
b bg 3+4+ 1+2+ 2 2 2 1+ 1-
bu r4- rr 2 2 1 1- 1+
e d
e ag 1+2+ 3-4- 1 2 1 1+ 1-
au 1-r 3+4+ 1 2 2 1- 1+
d bg 3+4+ 1-r 2 1 2 1+ 1-
bu 3-4- 1+2+ 2 1 1 1- 1+
(b) Simple induced corepresentations of the P4~/mnm' space group
r M Z A X R
a b
a ag 1+2+ 3+4+ 1 1 1 1+ 1-
au 1-r 3-4- 1 1 2 1- 1+
b bg 3+4+ 1+2+ 2 2 2 1+ 1-
bu r4- 1-2- 2 2 1 1- 1+
e ag 1+1+2+2+ l-l-rr 11 22 11 1+1-

au l-l-rr 1+1+2+2+ 11 22 22 1+1-
bg 3+3+4+4+ rr4-4- 22 11 22 1+1-
bu 3-r4-4- 3+3+4+4+ 22 11 11 1+1-
d a 1+2+1-r 1+2+1-r 11 22 12 1+1-

b 3+4+r4- 3+4+3-4- 22 11 12 1+1-
D~r
In units of (abe): a I (IOO), a2(010), a 3 (001)
Q: C2h (2/m) - a(OOO), b(O,O, 1/2), e(O, 1/2,0), d(O, 1/2, 1/2)
In units of (2n/a, 2n/b, 2n/e): hI (100), h2(01O), h3 (ool)
K: D2h - T(OOO), S(I/2, 1/2,0), Z(O,O, 1/2), R(I/2, 1/2, 1/2), X(I/2, 0, 0),
U(I/2,0,1/2)
P4~/mnm':
In units of (aae): a i (100), a 2(01O), a 3 (ool)
Q: D2h /C2h (m'm'm) - a(OOO), b(O,O, 1/2); C2h (2/m) - e(O, 1/2,0);
S,,/C 2 (4') - d(O, 1/2, 1/2).
In units of (2n/a, 2n/a, 2n/e): hI (loo), b2 (010), b 3 (ool)
K: 4'/mmm' - T(OOO), M(I/2, 1/2,0), Z(O,O, 1/2), A(I/2, 1/2, 1/2);
mmm - X(I/2, 0, 0), R(I/2,0, 1/2).
9.5 Corepresentations of the Space Groups of Antiferromagnetic La 2 Cu04 247
types (a), (b), (c), respectively. Steps (2) and (3) are written as
(2) DF,.!G., = a (3) (DF,.!Gq)jG = aiG
DI;,!Gq = 13 + 13 (DI;,!G.,)jG = (PiG) + (PiG)

DI;,!G., = (J + (J' (DI;,!Gq)jG = (JiG) + (J'iG)
(4) Find the symbol of the induced corep of S taking into account the types
of irreducible components of the induced rep obtained. One has to find among
the symbols of the induced rep of group G those which correspond to (a) type
irreducible coreps of S and pairs of symbols corresponding to (b) and (c) type
coreps: a" --+ DF,.", 13" + 13" --+ DI;,,,, (J" + (J~ --+ DI;,,, (or (J" + (Jao'" if the costar
of the wave vector k consists of two k-stars). Here the following notations are
used: a", 13", (J ,,(u), (J~(u) = (J ,,(ao 1 ua o ) for small irreps of G,,; DF,.", DI;,,,, DI;,,, for
small irreducible co reps of S" of types (a), (b), (c), respectively.
To generate a double-valued induced corep one may use the described
procedure for a double magnetic space group and induce from double site sym-
metry subgroups G.,.
As an example of induced corep generation we consider the magnetic group
P4~/mnm' = Dl:/Dil. In Table 9.6a simple induced reps of the unitary sub-
group Dil are given. As noted, the site symmetry groups of the magnetic group
are: unitary CZh for Wyckoff position c; black and white m'm'm (D 2h /C Zh ) for
positions a, band 4'(S4/CZ) for position d. Using the two different procedures
described for these two cases one obtains the simple induced co reps given in
Table 9.6b.
9.5 Corepresentations of the Space Groups

of Antiferromagnetic La2Cu04
In this section we generate the coreps of three magnetic symmetry space groups
of the antiferromagnetic phase of the La2Cu04 crystal, which is the basis ma-
terial of high-Tc oxide superconductors.
The structure of La Z Cu0 4 is tetragonal at high temperatures (T > 533 K)
and is described by the Fedorov space group G = Dll (I4/mmm). In Fig. 5.13
the disposition of atoms in tetragonal La Z Cu0 4 is shown. As was mentioned
in Sect. 6.3, the low-temperature orthorhombic phase with the space symmetry
Di: (Cmca) and doubled unit cell appears as a result of the Cu0 6 octahedron
tilting about the [110] direction of the tetragonal parent cell. For T> TN =
250 K the La 2 Cu0 4 crystal is paramagnetic but at T = TN a magnetic phase
transition to the antiferromagnetic phase takes place as a result of ordering of
the magnetic moments of the copper atoms. The direction of this ordering has not
been definitively found in experimental investigations [9.9, 10]. In Fig. 9.1
three possible magnetic structures of antiferromagnetic La2Cu04 are shown.
~--e (zp'--0 ~--(.;:\ Fig. 9.1. Three possible orientations of

~ r;(0(;'( I i~ >-I magnetic moments of copper atoms in
8-r-8 I
I '?T~-~ 0-~-e I the La 2 Cu0 4 crystal
I 1
1
le
J--ervl
b ,
I 1
I
I
,L-~- _I
10h ~ ,~2fl
I I I
I J-&,J
188-
1 181
I 1
f-;r-fe;il F~1 I f-- _7 1

A 1 ~ I 1 I 1 A 1 A
0= ~ -0
I I
I ~-+ 1:::' I 1 ~ _L):::!
~-t?e ~~-0 ~-~
In the first the magnetic moments of the copper atoms are oriented along the
(001) orthorhombic c-axis; this structure belongs to the Shubnikov space group
Cm' ca' - Dl:JCfh based on the ordinary (one-colored) base centered orthor-
hombic Bravais lattice. In the second structure, with magnetic space group
Pcmna - Dl:/Dih, the magnetic moments of the copper atoms are oriented along
the (100) orthorhombic a-axis. The orthorhombic Bravais lattice for this struc-
ture is black and white Pc type. The magnetic space group PAccn - Dl:JDl~
corresponds to the third magnetic structure and has a black and white orthor-
hombic Bravais lattice of PA type.
In the paramagnetic phase with the symmetry of Fedorov group Dl: the
origin of the coordinate system is chosen to be at the Wyckoff position a with the
site symmetry group Ga = C2h The coset representatives of Dl: in a decomposi-
Table 9.7. Single-valued and double-valued corepresentations of

the DWqh group
r Y Z R S T
a b
a a. 14 14 1 1 2 1 1
b au 23 23 1 2 1 1 1
a. 58 58 2 3 4 2 2
au 67 67 2 4 3 2 2
c a. 1144 2233 11 22 11 11
au 2233 1144 11 11 11 11
a. 5588 6677 22 44 22 22
au 6677 5588 22 33 22 22
e a 1122 1122 11 12 11 11
b 3344 3344 11 12 11 11
e(1) 5566 5566 22 34 22 22
e(2) 7788 7788 22 34 22 22
In (abc) units: U , (1/2, -1/2,0), u 2 (1/2, 1/2,0), u3(OOI)

Q: C2h /C i - a(OOO), b( -1/2,1/2,0); Ci - c(O, 1/2,0);
C2 - e(l/4 - y, 1/4 + y, 1/4).
In (2n/a, 2n/b, 2n/c) units: b , (1, -1,0), b 2 (1, 1,0), b 3(OOI)
K: D2h /C 2h - T(OOO), Y(I/2, 1/2,0), Z(O,O, 1/2), T( -1/2,1/2,1/2);
C2h /C i - R(O, 1/2, 1/2), S(O, 1/2,0)
9.5 Core presentations of the Space Groups of Antiferromagnetic La 2Cu04 249
Table 9.S. Single-valued and double-valued corepresentations of the Di: /Dih group
r X Y Z S T U R
a b a b
a. 1155 11 13 11 1 1 1 1 1 2
a a. 2266 11 24 22 1 2 2 1 2 I
b. 4488 22 24 22 I 2 2 I 1 2
b b. 3377 22 13 22 1 1 I 1 2 I
e-(1)
g 10 10 33 5 3 2 33 44 24 37 59
e-(2)
g 10 10 44 5 3 3 44 33 35 6,10 46
-(1)
e. 99 44 5 3 3 33 44 35 48 6,10
-(2) 99 33 5 3 2 44 33 24 59 37
e.
c a 12345678 1122 1234 1122 11 12 11 12

e 9999,10, 3333 5555 3333 22 33 2233 3456
10,10, 10 4444 33 44 4455 789, 10
e a 11227788 1122 1122 1122 11 12 11 12

b 33445566 1122 3344 1122 11 12 11 12
e(l)
99, 10, 10 3344 55 33 23 34 2233 349,10
e(2) 99, 10, 10 3344 55 33 23 34 4455 5678
"I
In (abc) units: (100), "2(010), "3(001)
Q: C2h - a(OOO), b(O, 1/2,0); C';CI - c(1/4, 1/4,0); C 2 - e(I/4, y, 1/4).
In (2n/a, 2n/b, 2n/c) units: b l (100), b2(01O), b3 (OOl)
K: D2h + aOD2h - r(OOO), X(I/2, 0, 0), Y(O, 1/2,0), Z(O,O, 1/2), S(1/2, 1/2,0), T(O, 1/2, 1/2),
U(1/2,0, 1/2), R(1/2, 1/2, 1/2)
Table 9.9 Single-valued and double-valued corepresentations of the Di:/Di~ group
r X Y Z S T U R
a b
a a. 1458 12 12 12 I 12 I 23 14
a. 2367 12 12 12 1 12 I 14 23
b ii. 10,10 3 34 34 2 3 2 5 6
ii. 99 3 34 34 2 3 2 6 5
c a 12345678 1122 1122 1122 11 1122 11 1234

e 9999, 10 3333 3333 3333 22 3333 22 5566
10, 10, 10 4444 4444 22 22
e a 11223344 1122 1122 1111 11 1122 11 1234

b 55667788 1122 1122 2222 11 1122 11 1234
e(l)
99,10,10 33 3344 3344 22 33 22 56
e(2) 3344 22
99, 10, 10 33 3344 22 33 56
"I
In (abc) units: (100), "2(010), "3(001)
Q: C2h /C, - a(OOO), b(O, 0,1/2); C';C I - c(O, 1/4, 1/4); C 2 - e(I/4, 1/4, y).
In (2n/a,2n/b,2n/c) units: bl(IOO), b 2 (010), b 3(001)
K: D2h + aOD2h - r(OOO), X(I/2, 0, 0), Y(O, 1/2,0); Z(O,O, 1/2), S(I/2, 1/2,0), T(O, 1/2, 1/2),
UO/2,0, 1/2), R(1/2, 1/2, 1/2)
tion relative to T (the translational group of the base-centered orthorhombic

Bravais lattice) are taken as
(9.S.1)
The improper translation v = (tH) is written in terms of the basic transla-

tion vectors of the base-centered orthorhombic lattice. The unit cell consists of
two formula units of La 2 Cu0 4 : two Cu atoms and four La atoms occupy
Wyckoff positions a and f, respectively, eight 0 atoms occupy e and f Wyckoff
positions.
The magnetic space groups may be written as
SIII = D~~/C~h = C~h + ao(UxIO)C~h ; (9.5.2a)
S{V = D~VDlh = Dlh + ao(Ell00)Dl h ; (9.S.2b)
S~v = D~~/D~~ = D~~ + ao(EIOOl)D~~ . (9.S.2c)
The site symmetry groups for Wyckoff positions of the space groups (9.S.2) are
both unitary C2h , for a, b-(9.S.2b), C2 e-all three groups (9.5.2), C; c-(9.S.2a)
and black and white C2h /C; a, b-(9.5.2a, c), CjC 1 c-(9.S.2b, c).
Using the procedure of induced corep generation described in Sect. 9.4, one
obtains single-valued and double-valued coreps of magnetic groups (9.S.2). The
induced coreps are given in Tables 9.7-9.
10. Site Symmetry in Permutation - Inversion Symmetry
Groups of Nonrigid Crystals
A crystal is called nonrigid if some of its nuclei show motions relative to

the crystal as a whole differing from small vibrations, for example, rotations,
inversion motions, or large amplitude vibrations. There are a great number of
such crystals [10.1]. For example, molecules in plastic crystals show free or
hindered rotations. These rotations can be observed, for instance, in NMR
spectra: one observes line narrowing when the molecules start to rotate.
Some nuclei in nonrigid crystals have no equilibrium position. Then it is
impossible to characterize the crystal symmetry by some space group. Similar
difficulties appear in the description of nonrigid molecules, such as ethane
C 2 H 6 , ammonia NH 3 , trimethylboride B(CH 3 h, etc. A useful definition of the
molecular symmetry group GM has been found, however, and widely applied
[10.2,3]. This is what we will be applying to crystals as well.
The Hamiltonian of a molecule is invariant under the operations of permu-
tations P of identical nuclei and inversion E* of the coordinates of all the
particles (nuclei and electrons) in the molecular center of mass. The molecular
symmetry group GM is defined as a group of permutation-inversion operations
P, p* = PE* = E* P corresponding to feasible (experimentally observable) mo-
tions of the particles in the molecule. The elements P, P* corresponding to the
motion of the molecule as a whole form a group isomorphic to the usual point
symmetry group of the molecule. An element P (or P*) corresponding to the
nonrigid motion connects two isoenergetic configurations of the molecule sepa-
rated (usually) by a potential barrier. If this barrier is overcome the element P
(or P*) has to be included in the symmetry group GM
The generation of a symmetry group for crystals on the basis of permuta-
tion-inversion elements is somewhat difficult as it is practically impossible to
label the nuclei by numbers and to describe the permutations by cycles usually
used for molecules [10.3]. Labeling by position vectors of the nuclei is more
suitable for crystals. The permutations of the nuclei can then be described by
means of point and space group elements [lOA]. This method of labeling and
describing the permutations allows one to obtain in general form the laws of
coordinate transformations under the elements of the permutation-inversion
symmetry group and to derive the relationship between the permutation-inver-
sion group of the crystal and its space group and the point symmetry group
of molecules in a nonrigid molecular crystal [10.5]. This approach can be also
applied for molecular symmetry groups.

252 10. Site Symmetry in Permutation - Inversion Symmetry Groups of Nonrigid Crystals
Permutation-inversion groups seem to be a particular interpretation of

the more general concept of color groups [10.6].
10.1 Symmetry Groups of Nonrigid Crystals
10.1.1 Labeling of Nuclei. Sampling of Coordinate Systems

Let us consider a plastic molecular crystal, i.e., a crystal with rotating molecules.
The discussion which follows is also applicable to crystals with other types of
nonrigid motion.
Let g = (Rlv + a.) E G be the space group of the initial crystal configura-
tion which is chosen as the most symmetrical one compatible with the feasible
motions of the nuclei. The abbreviations LSA and CSA denote the laboratory
system axes and the crystal system axes. The LSA are assumed to coincide with
the CSA in the initial configuration.
A rotating molecule which has its center of mass at the position
(j = 1,2, ... , t) (10.1.1)
in the initial configuration (in the CSA) is called the molecule q. Here, a i are
basic lattice translations and the vectors Wj determine the positions of molecules
inside the unit cell, t is the number of rotating molecules in the unit cell. The
nuclei of the crystal which are not in rotating molecules are also labeled by the
vectors q. The ends of all the vectors q form a system with space symmetry
group G' (G s G').
A rotating molecule q has its own symmetry described by the point group
1'1" Let q1 = q(O, 1) be one of the rotating molecules. The intersection G (\ 1'1
is a site symmetry group G'I. Let us decompose G into cosets with respect to G'I:
(10.1.2)
the sum is only over rotating molecules.

Let MSA q1 be the molecular system axes related to the rotating molecule
q1. Its orientation in the initial configuration is defined by the rotation w~~) [the
rotation w~~) brings the CSA in coincidence with MSA q1]. The orientation in
the initial configuration of other molecular systems axes MSA q is determined
by the rotations
or (10.1.3)
where Ry) and Rjll) are orthogonal parts of the operations g'l from (10.1.2) for
proper and improper rotations, respectively; m~l) is any improper rotation in
1'1. Thus w~O) are the matrices of proper rotations for all molecules q. Hence all
10.1 Symmetry Groups of Nonrigid Crystals 253
the MSA q are right-handed (or left-handed) and the orientation in the initial
configuration of the MSA q for translation ally equivalent molecules is the same.
The number of different rotation matrices w~o) does not exceed the number of
molecules in the unit cell.
Let the vectors
(10.1.4)
define the positions of the nuclei of a rotating molecule with respect to the
MSA q in the initial configuration (the same set of vectors p for all molecules
q). Therefore the position of a nucleus in CSA in the initial configuration is
obtained by the vector
Q = q + w~O)p = L nia i + Wj + w~O)p = (q,ft) (10.1.5)

i
We use the vector Q = (q,ft) as a nuclear label. For the nuclei which do not
belong to rotating molecules, P = 0 and Q = q.
10.1.2 Description of Permutation-Inversion Symmetry Elements

The operation g = (Rlv + a.) E G brings the crystal in the initial symmetrical
configuration in coincidence with itself. To generate a permutation group
isomorphous to G the element g E G must be mapped by the permutation which
moves the nucleus Q = (q,ft) into the position of the nucleus Q' = (q',p'):
Q' = q' + w~~)p' = g-l Q
= g-lq + W~~)lfW~~~f)-l R-IW~Op . (10.1.6)
Therefore we get
q' = g-lq , p' = m-l(q)p , m- (q) = (W(O-l Rw(O)
f g-lf
E M-f
(10. 1. 7)
This permutation, denoted as
[g,m(q)] , (10.1.8)
may be interpreted as the permutation of rotating molecules and the permuta-

tion of nuclei in molecules. Thus the permutation (10.1.8) formally defines the
nucleus replaced by the nucleus (qi,Pj) as follows:
(10.1.9)
Two permutations displace the nucleus (qi'P) into the position of the nucleus
[g2' m2(q)J [gl, m 1(q)J (q;,ftJ
= [g2, m2(q)] (gil q;, mil (qi)ftj ]

= (gil g2 1q;, mil (g2 1qJm21 (qJftJ
= [g2g1,m2(q)m 1(g2 1q)] (q;,ftJ . (10.1.10)
Therefore the composition law for permutations has the form
(10.1.11)
The set of permutations [g, m(q)], 9 E G, forms the group [G] isomorphic to G
(g ~ [g, m(q)]).
Now let us consider the set of permutations and permutation-inversion
operations compatible with feasible motions of the particles in a nonrigid crys-
tal (rotations and translations of a crystal as a whole, rotations of molecules),
[g,m(q)] , g=(Rlv+a.)EG' , m(q) E Mq ; (10.1.12)
Rand m(q) are both proper rotations,
[g, m(q)] * = [g, m(q)]E* , gEG' , (10.1.13)
and Rand m(q) are improper rotations.

It is obvious that the set of elements (10.1.12-13) forms a group gtlC' the
permutation-inversion group of a nonrigid crystal. The group gtlc has a
subgroup [Mq] with the elements [E,m(I)(q)b qq , + E(1 - b qq ,)], m(I)(q) E Mq,
isomorphous to the group M., of proper rotations of the molecule q (M., eM.,).
The direct product of the groups [M.,] for all rotating molecules q forms a
group
(10.1.14)
which is invariant in .0/'<" The latter is proved by direct calculation ({M} <J gtlJ.
Let us decompose the group .o/'c into cosets with respect to the invariant
subgroup {M}:
.o/'c = I
gEG'
[g,m(q)]{M} (10.1.15)
It is evident that the factor group gtlj{M} is isomorphous to the group G'. If the
representatives [g, m(q)] of co sets in (10.1.15) themselves form a group [G'], the
group &c has the form of a semi direct product
(10.1.16)
i.e., it is a wreath product of the groups [M,] and [G'].
10.1.3 Coordinate Transformations Induced

by Permutation-Inversion Symmetry Elements
Let us introduce the following notations: X, is a displacement from an equilib-

rium position with respect to the crystal system axes (CSA) of the rotating
molecule q as a whole or of the nucleus q which does not belong to the rotating
molecules; ~ Q (Q = q + OJ~O)jJ) is a displacement from the equilibrium position in
the molecular system axes (MSA) q of the nucleus p in the rotating molecule q;
OJ, is the direction-cosine matrix describing the orientation of the rotating mole-
cule q (or MSA q) with respect to the CSA; Q = Q(t/I, 9, cp) is the direction-cosine
matrix describing the rotation of the crystal as a whole; A is the displacement of
the crystal as a whole; r 'v is a position vector (in MSA q) of an electron v in the
rotating molecule q; rv is a position vector in CSA of an electron which does not
belong to the rotating molecules.
We consider as feasible the following motions of the system: rotation and
translation of the crystal as a whole (in LSA), rotation of the molecules (in CSA),
small vibrations of the rotating molecules' centers of masses (in CSA), small
vibrations of the nuclei in rotating molecules (in MSA q) and other nuclei (in
CSA), motion of electrons in molecules (in MSA) and in the crystal (in CSA).
Let us fix the system in some arbitrary configuration compatible with the
feasible motions of the particles of the crystal. This configuration is defined by
the set of variables X" ~ Q' OJ" Q, A. In this configuration the position of the
nucleus Q = (q,PJ is defined by the vector
(10.1.17)
The initial configuration is characterized by A = 0, Q = 1, OJ, = OJ~o>, X, = 0,

~Q = 0. The nucleus Q = (q,p) occupies, after the permutation [g, m(q)], the
position of the nucleus Q' = (g-lq,m-1(q)jJ):
L'Q = L Q, = A + Q{g-lq + Xg-I, + OJg_I,[m-1(q)p + ~Q']}

= A- QR-1(v + a.) + QR- 1{q + RXg-" + ROJg_I,m-1(q)[p + m(q)~Q']}
(10.1.18)
Hence
X~ = Px(g)X., = RXg-l., ; (10.1.19)
W~ = P",(g, m)W., = RWg_l.,m- 1 (q) ; (10.1.20)
~Q = P~(g, m)~ Q = m(q)~ Q' ,
(10.1.21)
r~v = Pr(g,m)r.,v = m(q)rg-l.,V in MSA q ; (10.1.22)
r~ = pr(g)r = grv in CSA . (10.1.23)
10.1.4 Site Symmetry Group of a Rotating Molecule in a Nonrigid Crystal

The site symmetry group {q} of a rotating molecule q in a nonrigid crystal
consists of the elements of the group ~c for which gq = q. The elements of the
group G' satisfying this condition form the site symmetry group G~. The group
{q} contains the subgroup {MI} (10.1.14) as an invariant subgroup. The factor
group {q}/{MI} is isomorphous to G~. If the representatives of co sets in the
decomposition
{q} = L [g,m(q)] {MI} , (10.1.24)
geG;'
form a group [Q~] then the group {q} has the form ofa semidirect product
{q} = {MI} 1\ [Q~] . (10.1.25)
When the problem depends on the variables related only to the rotating
molecule q, it is useful to consider the subgroup [q] of {q} with elements
[g(l), m(l)(q')] , [g(lI), m(II)(q')] * ,
(10.1.26)
g E G~ , m(q) E M., ;
or in simpler two-positional notation
(10.1.27)
,
g (I) g(lI) E ., ,
G'
The subgroup [MI.,] in [q] is also invariant and the factor group [q]/[MI.,]
is isomorphous to G~. The group [q] has the structure of a semidirect product
(10.1.28)
Under permutation-inversion operations of [q] the variables of the rotating

molecule q transform through themselves. The corresponding transformation
law follows from (10.1.18-22):
X~ = Px(g)X, = RX, ; (10.1.29)
w~ = Pw(g, m)w, = Rw,m- 1 (q) ; (10.1.30)
C;~ = Pz;(m)c;p = m(q)C;m-1(,)P ; (10.1.31)
r~v = P,(m)r 'v = m(q)r'v . (10.1.32)
The transformation law for rotation variables w was earlier obtained in

[10.7]. The group [q] is isomorphous to the subgroup of the direct product
M, x G, consisting of the products gm of the same parity (both proper or both
improper rotations). This is the group generated in [10.7]. However, in that
paper, M, is the full symmetry group of the molecule, here it may be a subgroup
if it contains the elements which are not compatible with feasible motions in the
system.
10.1.5 Permutation-Inversion Group of a Nonrigid Sodium Nitrate Crystal

The symmetry of the sodium nitrate crystal at low temperatures 548 K) is
described by the space group G = D~d [10.8]. At T> 548 K this crystal has a
new phase with the NO;- radicals rotating around the three-fold axes [10.1]. Let
us take the configuration of nuclei in the low-temperature phase (G = D~d) as
the initial symmetric one. Let the origin of the CSA be in the site of symmetry D3
and the y-axis be directed along one of the two-fold (horizontal) axes (Uy )'
Lattice translation vectors of the space group D~d are
3
a 1 = (a, 0, e) , a 2 ,3 = (-aI2, aj312,e) , a. = L niai'
i=1
(10.1.33)
The coset representatives in the decomposition of D~d with respect to the sub~
group of lattice translations are
(10.1.34a)
IX = (0,0, 3e/2) . (1O.1.34b)
The arrangement of nuclei and of symmetry elements is shown in Fig. 10.1.

The unit cell contains two formula units NaN0 3 [10.8]. The Na nuclei reside at
site b (0,0, 3e/4) of symmetry Gb = S6' The nuclei N (the centers of the
plane triangular radicals NO;-) occupy the Wyckoff position a [(0,0,0) and
(0,0,3e/2)] of symmetry Ga = D3 The oxygen nuclei are on the two-fold axes
(Wyckoff position e) at sites of symmetry C2 :
(O,uo,O), (=FV312uo, -uol2,O),
(0, -Uo, 3cl2), ( V312uo,uol2,3cl2) (10.1.35)

(a) (b) Fig. 10.1. Unit cell of the

sodium nitrate crystal and its
~~k,
symmetry elements
Uyi. Uyi. crxy
~ X2

Xl
b Yl
Oyi
Uvx , U vx , ax'j
Na eN 0 0
The MSA q I of the first radical (q I = (0,0,0)) is assumed to coincide with

CSA in the initial ~mmetric configuration (w~~) = 1). The plane radical NO:;
has the symmetry M = D3h with elements
- - -2 --2
E, C3 , C3 , iih , S3' S3,
(10.1.36)
Application of any operator (1O.1.34b) brings the first radical into coincidence
with the second one (q2 = (0,0, 3c/2. All these operations are improper rota-
tions. One of them with R = I is used to fix the orientation of the MSA q2 in the
initial symmetric configuration
(10.1.37)
All the translationally equivalent MSA are assumed to be identically oriented in

the initial symmetric configuration. The nuclei are labeled by their position
vectors in the initial symmetric configuration Q = q + w~o)p with the same Pfor
all the radicals:
P = Po = (0,0,0) for the nitrogen nucleus
P = PI = (O,uo,O) }
for oxygen nuclei (10.1.38)
P = P2,3 = (j3/2uo, -u o/2,0)
p=O for sodium nuclei .
The sodium nuclei and the centers of mass of radicals form the lattice of
symmetry G' = Djd'
Every operation (10.1.34) induces in all the MSA q the same operation
from the group M, = D3h :
E~E , til} ~ah ,

-2
C 3 ~C3 , t,.S6 ~ S3 ,
cj~Cj , 5
t"S6 ~ S3
-
,
(10.1.39)
Uy ~ Oy , t,.ay ~ ax ,
Uyx ~ OyX , t,.ayx ~ axy ,
Uyx~ OyX , t,.ayx ~ axy .
The permutation-inversion operations corresponding to the operations (10.1.34)

of the group G = D~d are represented in, the notation of (10.1.8) as follows:
[E, E(q)], [C 3, C3(q)], [ej, cj(q)],
[Uy, Oy(q)], [UyX' OyAq)], [UyX' Oyx(q)],

(10.1.40)
[t,.l, ah(q)]*, [t"S6' sj(q)]*, [t,.S~, S3(q)]*,
The permutation
[(Ela,,), E(q)] (10.1.41)
is related to a translation over a translation vector a".

The permutation-inversion operations (10.1.40,41) and their products form
a group [D~d] isomorphic to G = D~d. These operations bring the crystal into
configurations obtained from the initial one by a rotation or translation of
the crystal as a whole.
In the high-temperature phase the rotations of radicals about three-fold
axes in sodium nitrate appear to be feasible motions. Hence the permutations
(10.1.42)
must be included in the symmetry group of the system. The permutations

(10.1.42) with the identity operation form a group [(:3),] of nonrigid motions
of the radical q. The permutations corresponding to the rotations around two-
fold axes (Oy, OyX' Oyx) are not included in the group [M,] because such rota-
tions connect isoenergetic configurations separated by an insurmountable
barrier.
The group
(10.1.43)
is a group of pure nonrigid motions of nuclei in the sodium nitrate crystal. The
elements of this group correspond to various combinations of pure rotations of
radicals through the angles 2n/3 and 4n/3 around the three-fold axes, the crystal
as a whole being fixed. The permutation [til' E(q)] corresponds to a feasible
motion of the system (rotation through n of all the radicals about vertical axes
and translation by -IX of the crystal as a whole). The elements of [D~d]
(10.1.40,41) and their products with [tll,E(q)] form the permutation-inversion
group [Djd]. Thus, the permutation-inversion group of the nonrigid sodium
nitrate crystal may be written as fl'c = {C 3 } A [DjdJ.
10.2 Irreducible Representations

of a Nonrigid Crystal Symmetry Group
Since a symmetry group fl'c of a nonrigid crystal contains an invariant subgroup

{MI} (10.1.14), the method of little groups (Sect. 2.3.4) may be used to generate
its irreps. We consider this procedure using the example of the permutation-
inversion group of a nonrigid sodium nitrate crystal.
10.2.1 Generation of Irreducible Representations

The invariant subgroup {MI} of fl'c in a nonrigid NaN0 3 crystal is a direct
product of [MI,] isomorphic to the point group C 3 . An irrep of {MI} is defined
by the symbols (a, e(1), e(2 of [Mlf] +-+ C3 ordered in the sequence of the groups
[MI f] in the direct product. In the model of an infinite crystal the group {MI} has
an infinite set of irreps with labels in the form of an infinite three-dimensional
sequence of symbols a, ell), e(2).
To define stars of irreps let us note that m- l Em = E, m- l C3 m = C3 or cj,
and m-ICjm = cj or C3 for mE D 3d Thus, the element [E,m-Im(l)m(g-lq)]
conjugated to the element [E, m(I)(q)] by means of [g, m(q)] has, at position q,
an operation which is at position gq in the element [E,m(l)(q)] with possible
substitution C3 +-+ cj. Therefore the label of an irrep conjugate to some initial
one by means of an element [g, m(q)] is obtained from the latter by substitution
of the symbol at position q by the symbol at position gq with possible substitu-
tion ell) +-+ e(2).
The identity irrep of {MI} forms a star on its own. The corresponding little
group Q coincides with the full group fl'c (Q = fl'c)' Its small irreps are generated
by the irreps of the space group Djd (fl'c/{MI} +-+ Djd) and are a part of all the
group fl'c irreps. In these irreps all the elements of the coset [g, m(q)] {MI} are
mapped by the single matrix which is the matrix of the element [g, m(q)] E [Djd]
in one of the irreps of the group [Djd] +-+ Djd. Just these irreps of fl'c assure the
necessary symmetry of wave functions of the crystal with respect to the permu-
tations of identical oxygen nuclei in the radicals (Sect. 10.2.3). The other irreps
do not correspond to realizable states of the crystal and, therefore, are not
considered here.
10.2 Irreducible Representations of a Nonrigid Crystal Symmetry Group 261
10.2.2 Irreducible Representations of a Site Symmetry Group

The rotating molecules in nonrigid crystals have a certain degree of indepen-
dence. One may consider the states of molecules which can then be used to
generate the wave functions of the whole crystal. The states of the rotating
molecule are eigenstates of a Hamiltonian H" with the symmetry defined by the
site symmetry group [q] (Sect. 10.1.4). In the approximation of total decoupling
of different degrees of freedom the wave functions have the form
(10.2.1)
where the factors describe the rotation of the molecule as a whole t1>iw,,),
electronic motion Rv(r ,,), internal vibrations Xk( ~ Q), vibrations of the molecular
center of mass Xt(X,,) and nuclear spin motion A y
The irreps of the group [q] are the basis for the classification of all the
factors in (10.2.1) and of the whole function tp(,,) in the frame of a single group.
The little group method may be used to generate the irreps of the site symmetry
group [q].
In the case of a NaN0 3 crystal the group [q] is a semi direct product
(10.1.28). Three irreps of the group [C3 ] <l [q] are partitioned into two stars:
a and e = (e(1), e(2. For the star a the little group Q coincides with the whole
group [q] and its small irreps are related in the usual way to the irreps of
[D 3d ]. To label these irreps of the group [q] we use the star symbol a and the
label of irreps of the group [D3d]'
For the star e the little group is
(10.2.2)
Its small irreps are related to the irreps of the group [S6]. Their induction to the
group [q] generates six more two-dimensional irreps of [q]. These irreps are
labeled by the symbol e of the star and the symbols of the irreps of the group
[S6]. The characters of all the irreps of the group [q] are given in Table 10.1,
where the elements of the group are numbered as follows:
[E,E] - 1 ,. [E, c 3] - 13 ; [E,Cn - 25 ;
-2
[C 3 , C3 ] - 2', [C 3 , C3] - 14 ; [C 3 ,E] - 26 ;
[C~,Cn - 3 ; [q,E] - 15 ; [C~, C3 ] - 27 ;
[Uy , Uy ] - 4', [Uy , Uyx ] - 16 ; [Uy , Uyx ] - 28 ;
[UyX ' Uyx ] - 5 ,. [UyX ' Uy ] - 17 ; [UyX ' Uyx ] - 29 ;
[UyX ' Uyx ] - 6', [UyX ' Uyx ] - 18 ; [Uyx , Uy ] - 30 ;
[1, uz ]* - 7', [1, S3]* - 19 ; [1,Sn* - 31 ;

5 -
[S6,S3]* - 8 ; [S~,S~]* - 20 ; [S~, uz ]* - 32 ;
Table 10.1. Characters ofirreducib\e representations of the group [C,J /\ [D3dJ tv
0-
N
1 2 3 4 5 6 7 8 9 10 11 12 13 14 \5 \6 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
aa 1g \ 1 1 1 1 1 1 1 \ 1 1 1 \ \ 1 1 1 1 1 1 1 \ 1 1 \ \ \ 1 1 1 1 1 \ 1 1 1 p
aa 2g \ 1 \ -\ - \ -1 1 \ 1 -1 -1 -1 1 1 \ -\ -1 -\ 1 \ 1 -1 -1 - \ 1 1 1 -1 -1 -\ 1 \ 1 -1 -1 -\
aa ltl 1 1 1 \ 1 1 -1 -1 -1 - \ -1 -1 1 1 1 1 1 1 -1 -1 -1 -1 -1 -1 1 1 1 1 1 1 -1 -1 -\ -1 -1 -1 ~
aa 2u 1 1 \ -1 -\ -1 -1 -1 -1 1 \ 1 1 1 1 -\ -1 -1 -1 -1 -\ 1 1 \ \ \ 1 -1 - \ -1 -1 -1 -1 \ \ 1 "en
'<
aeg 2 -1 -1 0 0 0 2 -1 -1 0 0 0 2 -1 -1 0 0 0 2 -1 -1 0 0 0 2 -1 -1 0 0 0 2 -1 -\ 0 0 0
ae. 2 - \ -\ 0 0 o -2 1 1 0 0 0 2 -1 -1 0 0 o -2 1 \ 0 0 0 2 -\ -1 0 0 o -2 1 1 0 0 0
2 2 2 0 0 0 2 2 2 0 0 o -1 -1 -1 0 0 o -1 -1 -1 0 0 o -1 -1 -1 0 0 o -1 -1 -\ 0 0 0
ea,
2 2 2 0 0 o -2 -2 -2 0 0 o -1 -1 -\ 0 0 0 1 1 1 0 0 o -1 -1 -1 0 0 0 1 1 1 0 0 0
I...
'<
ea. S
ee!ll 2 -1 -1 0 0 0 2 -1 -1 0 0 o -1 -1 2 0 0 o -1 -\ 2 0 0 o -1 2 -1 0 0 o -1 2 -1 0 0 0
ee~2) 2 -1 -1 0 0 0 2 -1 -1 0 0 o -1 2 -1 0 0 o -1 2 -1 0 0 o -1 -1 2 0 0 o -1 -1 2 0 0 0 ~
ee~l) 2 -1 -1 0 0 o -2 1 \ 0 0 o -\ -1 2 0 0 0 1 \ -2 0 0 o -1 2 -1 0 0 0 \ -2 \ 0 0 0 3s::
ee~2) 2 -1 -1 0 0 o -2 1 1 0 0 o -1 2 -1 0 0 0 1 -2 1 0 0 o -1 -1 2 0 0 0 1 1 -2 0 0 0 g
0'
I:>
rp -rp rp+n -rp +n rp + 4n/3 -rp + 4n/3 rp + n/3 -rp + n/3 rp + 2n/3 -rp + 2n/3 rp + 5n/3 -rp + 5n/3 I
S"
"'~."
o
I:>
en
'<
3
3
~
...
'<
Cl
...
o
s::
'1j
'"o
..,
Z
o
I:>
::!.
CS.
0-
n
...
'<
'"
:
'"
10.2 Irreducible Representations of a Nonrigid Crystal Symmetry Group 263
[S6,8D* 9 [S6' O'z]* - 21 [S6,83]* 33
[<Ty, O'x] * 10 [<Ty,O'XY]* - 22 [<Ty,O'XY]* 34
[<TyX'O'XY]* - 11 [<Tyx,O'XY]* - 23 [<TyX'O'x]* - 35
[<TyX'O'XY]* - 12 [<TyX'O'x]* - 24 ; [<TyX'O'XY]* - 36 (10.2.3)
10.2.3 Classification of States

The multipliers in (10.2.1) are classified according to subgroups of [q] isomor-
phic to the groups of operators Pro, P" Pt;, Px (10.1.29-32). The action of opera-
tors Px on the coordinates XIJ is uniquely determined by the operations which
are in the first position in the two-positional notation of the group [q] elements
given in (10.2.3). The set of operations Px forms a group isomorphic to the point
group D 3d . The action of the operators P, is defined by the second operations
in this notation of the group [q] elements. These operators form a group
isomorphic to the point group MIJ = D 3h . The operators PI; are Wigner's
operations for nuclear displacements and also form a group isomorphic to
MIJ = D 3h The transformation of the rotational variable cp under the operators
Pcp = Pro is given in the last row of Table 10.1. The elements
[E, E], [E, C3], [E, CD, [Uy, Uy], [Uy, Uyx ], [Uy, Uyx ],
[I,O'z]*, [1,83]*, [I,8D*,
(10.2.4)
form a subgroup isomorphic to D3h (or D 3d , or D6)' The operators Pcp corre-
sponding to these elements are different and also form a group isomorphic to
D 3h . In the total list of 36 operators Pcp, each of 12 operators is repeated three
times. This fact permits one to choose the irreps of [q] which may describe the
transformation properties of rotational wave functions cPl'(w) = cPl'(cp).
The irreps of [q] according to which the wave functions depending on other
variables transform may be defined in the same way. This is shown in Table
10.2 for the case of nitrate radicals in NaN0 3
Table 10.2. Possible symmetry types for different

motions of NO:J radicals in nonrigid sodium
nitrate crystals
Wave functions Symmetry types
X,(Xf ) aa 1g , aa 2g , aa t ,., aa 2u , ae g , aeu

<p"(cp.) aa 1g , aa 29 , aa lu , aa 2u , ea g , ea"
Xk(~ Q) aa 1g , aa 29 , aa 1", aa 2u , ee f(1) ,ee (1)
u
R.(r.) aa 1g , aa 2g , aa 1u , aa 2u , ee g1), eeL!)
.1,(a) aa 1g
The oxygen nuclei are bosons with spin s = O. The wave function Ay
describing the state of nuclear spins in radicals transforms according to aa 1g of
the group [q].
With respect to the permutations of identical oxygen nuclei from the group
[C\] the wave function (10.2.1) should transform according to the irrep a.
Hence the wave functions compatible with this symmetry may transform only
according to those irreps of the group [q] which are characterized by the star a.
The possible symmetries for excitations of one type of motion (electronic, rota-
tional, etc.) are given directly in Table 10.2.
To determine the possible symmetry types of combined excitations it is
necessary to form the direct products of irreps from Table 10.2 and to pick out
those which contain the irreducible components with the star a.
The product of molecular functions (10.2.1) with the star a is a fun2tion
which spans the space of identity irrep ... x a x a x a ... of the group {tW1I} <J
&'C. The corresponding irreps of &'C are generated and briefly discussed in Sect.
10.2.1.
10.3 Generalized Symmetry of High-Temperature Phase

of Fullerite C 60
A new modification of carbon in the form of neutral clusters Cn with n ~ 60

has been revealed experimentally in 1984 [10.9]. The molecules Cn (n~60)
were named fullerenes and crystals formed with these molecules were called
fullerites. The interest in these objects is due to a number of significant proper-
ties of fullerenes and fullerites [10.10] and, in particular, due to superconduc-
tivity of fullerite doped with alkali metals M3C60 [10.11]. The simplest of
fullerenes is the molecule C60 which has the form of a truncated icosahedron
with 12 pentagons and 20 hexagons as sides. This molecule has six fivefold in-
version axes, ten threefold inversion axes and fifteen twofold symmetry axes.
Its point symmetry group is Y h (Table 3.1).
Two phases of crystalline fullerite C60 are known. A first-order phase
transition takes place at T z 249 K. The symmetry of the low-temperature
phase is shown to be T~ (P2 j /a3) [10.12]. In a high temperature orienta-
tionally disordered phase the centers of rotating molecules C 60 form a face-
centered cubic lattice and occupy the positions q = n. The symmetry of this
phase is determined as T~ (Fm3) in [10.13] and as Oh (Fm3m) in [10.14].
However the crystals with rotating molecules are related to nonrigid crystals.
Their symmetry can be described only in the frame of the group of generalized
(coloured) symmetry. In following subsections we generate the permutation-
inversion symmetry group Pc of nonrigid fullerite C60 , study their irreps and
classify the states of the crystal.
10.3 Generalized Symmetry of High-Temperature Phase of Fullerite C60 265
10.3.1 Permutation-Inversion Symmetry Group of Fullerite C60

in the High-Temperature Phase
Following Sect. 10.1 in the case of nonrigid fullerite C60 we represent permu-
tation-inversion operations with the help of space group operations gEO~ and
point-group operations mEYh. The group Pc consists of the elements
[g,m(n)), [/g,Im(n)]*, g,IgEO~; m,ImEYh . (10.3.1)
The elements [g,E(n)], [/g,I(n)] * (g,IgEO~) correspond to the permutations

of the molecules as a whole. They form the permutation-inversion group
[O~] isomorphic with the space group O~. The operations [E,m(n')onn'+
E(n')(l-onn ,)](mEY) correspond to the permutations of nuclei of the mole-
cule in the site n. They compose the group [Y(n)] .... Y. Denote the direct prod-
ucts of [Y(n)] by {Y}.
It is easy to see that Pc has the form of a direct product
(10.3.2)
A site symmetry group {n} of a rotating molecule at the site n consists of

those elements of Pc for which gn = n. It also has the form of a direct prod-
uct
{n}= [Oh(n)]x{Y} , (10.3.3)
where [Oh(n)] denotes the permutation-inversion group isomorphous to the

point group Oh (n) (site symmetry group of the Wyckoff position a in the
space group O~, occupied by the molecule in the site n. When the problem
depends on the variables related only to this molecule it is useful to consider
the subgroup [n] of {n}.
[n] = [Oh(n)] x [Y(n)] = [O(n)]x[Y(n)]x[C;(n)] (10.3.4)
10.3.2 Irreducible Representations of the Groups [n] and Pc

Irreps of [n] are obviously the direct products of the irreps of the groups
[O(n)], [Y(n)] and [C;(n)]. We denote the irreps of [n] by the triple indexes
consisting of the irreps symbols for the groups [O(n)), [Y(n)], [C;(n)]:
d(Y) = a, t 1, t 2, g , h', d(C) = g, u (10.3.5)
The irreps for Pc can be also generated as direct products of the irreps of
the groups [O~] and {Y}. However the wave functions of a crystal (forming
the space of some irrep of its symmetry group Pc) have to satisfy the principle
of symmetry with respect to the permutations of identical c,arbon nuclei
(bozon type particles with the zero spin). Let us assume that an approximate
wave function has the form of a product (or a sum of products) of wave func-
tions of all the molecules C60 To satisfy the above mentioned principle the
wave function of a molecule in the site n has to be symmetrical under permuta-
tions corresponding to the rotations of the molecule relatively to the crystal,
i.e., it has to transform according to the unit rep a of the group [Y(n).
Therefore, in the frame of the group [n], it may transform according to any
representation of the type (d(O), a, d(C, i.e., according to any rep of the site
symmetry group Oh of the Wyckoff position a in crystalline lattice with space
group O~.
It is possible not to symmetrize the crystal wave function on the whole.
This may be argued as follows. Let us consider a finite but macroscopic crystal
as a gigantic molecule. It has three rotation degrees of freedom, but its
moments of inertia I j are macroscopic values (in the limit Ir> 00). Therefore
its rotational constants B j = fz2/(2~) are very small (in the limit Br-+O) and a
rotational structure of spectra (due to the rotation of the crystal as a whole)
can not be revealed experimentally. There are no limitations on the symmetry
of a wave function of the crystal without its rotational part, as it is always
possible to select the rotational part so that the whole wave function of the
crystal should satisfy the principle of symmetry with respect to the permuta-
tions of identical nuclei. When taking into account this principle the set of ir-
reps for classifying the states of the crystal (without its translation and rotation
as a whole) coincides with that of the space group O~.
10.3.3 Classification of States of Nonrigid Fullerite C 60

An approximate wave function of the crystal's ground state can be written as
a product of the molecular ground states
lfIo = II <Po (n) (10.3.6)

n
Low-lying excited states of the crystal in the same approximation have the
form of Bloch waves
(10.3.7)
n n'*n
where <Pi(n) are wave functions of excited states of the molecule in the site n.
In the approximation of total decoupling of different degrees of freedom the
molecular wave functions <Pi (n) have the form of the product
(10.3.8)
10.3 Generalized Symmetry of High-Temperature Phase of Fullerite C 60 267
of the functions describing vibrations (Xt ) and rotations (r[>,J of the molecule
as a whole, internal vibrations Cxd and electronic motions (Rv) in the
molecule. The laws of coordinate transformations under permutation-inver-
sion operations (10.1.29 - 32) determine the possible symmetry types (irreps of
[n]) of the functions describing different motions of the molecule C60 in the
fullerite crystal: X t according to (d(O),a,d(C); r[>11 according to
(d(O),d(Y),g); Xk and Rv according to (a,d(Y),d(C).
As the wave function of the molecule on the whole may be of the sym-
metries (d(O), a, d(C;)) then the symmetry of the pure excitations of one type
of motions are the following:
(d(O), a, d(C) for vibrations of the molecule as a whole;
(d(O),a,g) for rotations of the molecule; (10.3.9)
(a,a,d(C) for internal vibrations and electronic motions.
The excitations of other types can exist in a crystal (and can be revealed in
spectra) only as combined ones.
References
Chapter 1
l.1 S.c. Miller, W.F. Love: Tables of Irreducible Representations of Space

Groups and Co-Representations of Magnetic Space Groups (Pruett, Boulder,
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l.2 C.J. Bradley, A.P. Cracknell: The Mathematical Theory of Symmetry in Solids
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Chapter 6
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8.33 LP. Ipatova, Yu.E. Kitaev, V.G. Malyshkin, R.A. Evarestov: Fiz. Tverd. Tela
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8.36 Yu.E. Kitaev, M.F. Limonov, A.G. Panfilov, R.A. Evarestov, A.P. Mirgorod-
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[English trans!.: SOY. Phys. - JETP 79, 973 (1994)]
8.38 Yu.E. Kitaev, L.V. Laisheva, M.F. Limonov, H. Lichtenstern, A.P. Mirgorod-
sky, R.A. Evarestov: Physica C 245,48 (1995)
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8.42 Yu.E. Kitaev, L.V. Laisheva, M.F. Limonov, T.!. Maksimova, R.A. Evarestov,
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Chapter 9
9.1 C.J. Bradley, A.P. Cracknell. The Mathematical Theory of Symmetry in Solids
9.2 V.A. Koptsik: Shubnikovskiye Gruppy (Moscow State University, Moscow
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Subject Index
Accidental degeneracy 59 Clebsch-Gordan decomposition 18

Additional degeneracy 155 Cluster model of crystals 179
Adiabatic approximation 125 Cluster model of imperfect crystals 188
Angular momentum 61 Compatibility relations
Antiferromagnetic crystal 239 - for irreducible representations of D 11, 86
Antiunitary operation 237 Composition law 5
Associativity 5 Composite induced representation 98
Atomic contributions to crystalline states in Conditional product of groups 8
high-temperature superconductors 165, Conjugacy class 7
166, 170 Conjugate element 7
Axial vector 62 Construction of hybrid orbitals 135
Axial vector representation 207 Corepresentation 242
Axis - induced 244
bilateral 40 Correlation table 89
equivalent 40 Coulomb operator 127, 128
inversion 40 Criterion
n-fold 39 - chain 206
n-fold mirror rotation 39 - of irreducibility of a representation 13,
15
Band model of imperfect crystals 189, 190 - of reality of an irreducible
Band representation 97 representation 17
- of space group 97 subgroup 205
Basic domain 75 - subduction 205
Basis of a representation 10 - tensor field 206
Binary algebraic operation 5 Critical symmetry point 215
Black and white Crystalline class 44
- Bravais lattice 237 Crystallographic orbit 49
- space group 237 Crystal structure types 107, 108, 111, 113,
Bloch function 73, 147 114,117,118,124
Bravais lattice type 43 Crystal system 43, 192
base-centered 44 Cyclic boundary conditions 46
body-centered 44 Cyclic model of imperfect crystals 189
face-centered 44
primitive 44 Decomposition of representations 15, 16
Brillouin zone Decomposition of groups 7
- of a simple orthogonal lattice 75 Defects 185
Cayley-Klein parameters 34 Defining elements 6
Canonical basis 60 Density of states 157
Canonical wave vector 76 Dimension of a representation 10
Character Diperiodic groups 192
of an element in a representation 13 Direct sum of representations 12
- of a representation 13 Direct product
- of an induced representation 23, 24 of groups 8
Class 7 - of matrices 18
278 Subject Index
Direct product (cont.) site 40, 48

- of representations 18 space 44
- of spaces 17 translation 31, 43
Disjoint classes 7 wave-vector point symmetry 74
Double group 66
Hartree-Fock equations 127, 128
Eigenstate 55 Herring's approach 79
Electron density matrix 128 Homomorphism of groups 9
Energy band 145 Homomorphous mapping 10
degenerate 145 Hybridized orbitals
conduction 145 in molecules 137, 139
forbidden 145 - in crystals 160
many-ellipsoidal 155
many-valleyed 155 Identity element 5
simple (nondegenerate) 145 Image of an element 10
valence 145 Index of an induced representation
Energy lacuna 203 - in q-basis 93
Equivalent Hamiltonians 146 - in k-basis 95
Equivalent wave vectors 73, 74 Index of a subgroup in a group 6
Euler angles 33 Induced corepresentation 244
Exchange operator 127, 128 Inner translation 46
International notation of point groups 40
Factor-group 7 International symbol of a space group
Factor-system 30, 79 45
F-aggregate center 187 Interpolation scheme
Ferromagnetic crystal 238 - on the basis of localized functions 175
Fractional translation 45 - Slater-Koster's 175
Fullerenes 264 Intertwinning numbers 96
Fullerites 264 Irreducible part of the Brillouin zone 76
Inverse element 5
Generating element 6 Inversion operator 35
Generating point of a crystallographic or- Inversion operation E* 251
bit 48 Isomorphism of groups 10
Generating relations 6 Isotropy subgroup 205, 209
Glide reflection plane 39
Gray site symmetry group 239 k-basis 73
Gray space group 237 - of an induced representation 93
Group 5 Kernel of the homomorphism 10
Abelian 6 k-p pertubation method 147
commutative 6
continuous 6 Labelling of small representations 82
crystallographic point 39 Landau condition 206
cyclic 6 Lattice vector 45
Euclidean 31 Layer groups 192
"extended" rotation 61 Left coset 6
finite 6 Lifshitz condition 206
full orthogonal 35 Linear transformation of basis translation
holosymmetric point group 43 vectors 46
infinite 6 - symmetric 47
inversion 35 Line of symmetry 75
little 27 Little group method 26
modulo 8 - of wave vector 76
normal 7 Local exchange potential 129
orbital 42 Localized orbitals
permutation 42 in crystals 159, 174
rotation 32 - in molecules 137, 138, 141, 143
Subject Index 279
Mackey's subgroup theorem 96 Polar vector 62

Main region 48 Principal axis 39
Mapping 10 Projection operator 16
Model of an infinite crystal 43 Product of groups
Matrix representation 11 conditional 8
Maximal isotropy subgroup 98 direct 8
Mirror reflection plane 36 semi-direct 8
Mirror rotation 36 weak direct 8
MO LCAO approximation 133 Proper rotation 35
Molecular cluster approach 188 Pseudovector 62
Molecular symmetry group 251 Pure translation 44
Multicentered bonds 140
Multiplication 5 Quasi-diagonal structure
Multiplication law modulo 47 - of a representation matrix 12, 56
Multiplication table 6 - of a Hamiltonian 57
of the double point groups 15, 15h 68 q-basis 93
of the double point groups 0, 0h 67 Quotient group 7
of the point groups D, Dh 68 Reciprocal element 5
of the point groups 0, 0h 67 Reciprocal lattice vector 73
Multiplicity of a representation 12 Reciprocity (Frobenius) theorem 25, 95
Reduction coefficients 21
Nonrigid crystal 251 Reduction matrix 25
Normalization factor 21, 25 Re-isomorphic space group 238
Normalizer 7 Relation between
Notation of the small irreps 81 - rotation parameters 33
- setting dependence 82 - crystallographic point groups 62
Representation (rep) 10
One-determinant approximation 127 induced
Operation of antisymmetry 237 characters for space groups 95
Orbit 42 - of crystallographic point groups 90
Order of a group 6 - symbol in k-basis for space groups 95
Order of an element 6 irreducible (irrep) 12
Order parameter 205 double-valued of point groups 71, 72
Oriented site symmetry group 51 of a translation group 73
Origin choice 82 of point groups 63, 64
Orthogonality relations of space group D 1t 85
- for characters of irreducible representa- of SU(2) group 60
tions 13 of the full orthogonal group 61
- for the matrix elements of unitary of the rotation group 60
representations 13 unit 12
Representation domain 76
Periodic boundary conditions 46 Representative of a coset 7
Permutation-inversion group 254 Resonance surface states 203
- of nonrigid NaN0 3 crystal 260 Restriction of a representation 26
Permutation representation 206 Reverse effective mass tensor 154
Phonon symmetry Right coset 7
- in superlattices 223, 224 Rotation 32
- in high-temperature superconduc- improper 35
tors 228, 235 mirror 36
Physically irreducible representation 59 parameter 33
Plain groups 191 proper 35
Plane of symmetry 75
Point defects 185, 186 Schmidt's procedure of orthogonaliza-
- of molecular type 186 tion 15
Point group of a wave vector 76 Schonflies notation of a point group 40
Point of symmetry 75, 195 Schonflies symbol of a space group 45
280 Subject Index
Schrodinger equation 55 Symmetry-adapted basis 15

Schur's lemmas 13 - - vectors 25
Screw rotation 38 Symmetry information about a molecule 42
Second-order phase transition 205 Symmetry of localized orbitals
Seitz symbol of an operation 44, 51 in crystals 161, 162, 163, 164
Selection rules 214 - in molecules 137, 140, 142, 143
- for infrared spectra 214 - in high-temperature superconduc-
- for Raman spectra 214 tors 167,169,171
Selfconjugate element 7 Symmetry operation
Self-consistent field method 127 of a Hamiltonian 55
Semi-direct products of groups 8 of a linear molecule 40
Semi-infinite crystal model 191 of a molecule 40
Set K 94 of a SchrOdinger equation 55
Set Q 98 Syngony 43, 192
Setting 52
Site symmetry group 40, 48, 195 Time-reversal transformation 57
- in a nonrigid crystal 256 Translation group 31
Simple induced representation 97 Translation operator 31
- of space groups 102, 106 - 120 Translation vector 43, 192
Single defect model 186
Single crystal family 216 Unit cell 44
Slab model 191 base-centered 44
Space group body-centered 44
- symmorphic 45 conventional 44
- nonsymmorphic 45 crystallographic 44
Space group setting 82 elementary 43
Space of a representation 10 face-centered 44
Special points 174 fundamental 43
sp3-hybridization 138 large 46
Spinor rank 61 primitive 44
Square of an irrep 19 Wigner-Seitz 44, 195
- symmetrical 19 volume 43
- antisymmetrical 20
Subduction frequencies 96 Unit element 5
Subgroup 6
invariant 7 Van-Hove's singularities 158
- normal 7, 10 Vibrational field representation 210
- unitary 237
Shubnikov points groups 238 Wave vector 73
Shubnikov space groups 237 Wigner's theorem 57
Sub lattice 92 Wreath product 255
Subspace 12 Wyckoff position with free parameters 49,
Superiattices 215 51
Supplementary translation 38
Star of a wave vector 76 Zero-slope point 151
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and Superlattices and Nonequilibrium Systems Editor: M. Suzuki
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54 Magnetic Excitations and Fluctuations Semiconductors 2nd Edition
Editors: S. W. Lovesey, U. Balucani, F. Borsa, By M. L. Cohen and J. R. Chelikowsky
and V. Tognetti 76 Electronic Properties of Conjugated Polymers
55 The Theory of Magnetism II Thermodynamics Editors: H. Kuzmany, M. Mehring, and S. Roth
and Statistical Mechanics By D. C. Mattis 77 Fermi Surface Effects
56 Spin Fluctuations in Itinerant Electron Editors: J. Kondo and A. Yoshimori
Magnetism By T. Moriya 78 Group Theory and Its Applications in Physics
57 Polycrystalline Semiconductors 2nd Edition
Physical Properties and Applications By T. Inui, Y. Tanabe, and Y. Dnodera
Editor: G. Harbeke 79 Elementary Excitations in Quantum Fluids
58 The Recursion Method and Its Applications Editors: K. Ohbayashi and M. Watabe
Editors: D. G. Pettifor and D. L. Weaire 80 Monte Carlo Simulation in Statistical Physics
59 Dynamical Processes and Ordering on Solid An Introduction 2nd Edition
Surfaces Editors: A. Yoshimori and By K. Binder and D. W. Heermann
M. Tsukada 81 Core-Level Spectroscopy in Condensed Systems
60 Excitonic Processes in Solids Editors: J. Kanamori and A. Kotani
By M. Ueta, H. Kanzaki, K. Kobayashi, 82 Photoelectron Spectroscopy
Y. Toyozawa, and E. Hanamura Principle and Applications 2nd Edition
61 Localization, Interaction, and Transport By S. HUfner
Phenomena Editors: B. Kramer, G. Bergmann, 83 Physics and Technology of Submicron
and Y. Bruynseraede Structures
62 Theory of Heavy Fermions and Valence Editors: H. Heinrich, G. Bauer, and F. Kuchar
Fluctuations Editors: T. Kasuya and T. Saso 84 Beyond the Crystalline State An Emerging
63 Electronic Properties of Perspective By G. Venkataraman, D. Sahoo,
Polymers and Related Compounds and V. Balakrishnan
Editors: H. Kuzmany, M. Mehring. and S. Roth 85 The Quantum Hall Effects
64 Symmetries in Physics Group Theory Fractional and Integral 2nd Edition
Applied to Physical Problems 2nd Edition By T. Chakraborty and P. Pietilainen
By W. Ludwig and C. Falter 86 The Quantum Statistics of Dynamic Processes
65 Phonons: Theory and Experiments II By E. Fick and G. Sauermann
Experiments and Interpretation of 87 High Magnetic Fields in Semiconductor
Experimental Results By P. Brliesch Physics II
66 Phonons: Theory and Experimeuts III Transport and Optics Editor: G. Landwehr
Phenomena Related to Phonons 88 Organic Superconductors
By P. BrUesch By T. Ishiguro and K. Yamaji
67 Two-Dimeusioual Systems: Physics 89 Strong Correlation and Superconductivity
aud New Devices Editors: H. Fukuyama, S. Maekawa, and
Editors: G. Bauer, F. Kuchar, and H. Heinrich A. P. Malozemoff
68 Phonon Scattering in Condensed Matter V
Editors: A. C. Anderson and J. P. Wolfe

(Professor Robert A. Evarestov, Professor Vyaches

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108 Springer Series in Solid-State Sciences

Edited by Manuel Cardona

90 Earlier and Recent Aspects 108 Site Symmetry in Crystals

Professor Vyacheslav P. Smirnov

Library of Congress Cataloging-in-Publication Data.

St. Petersburg, July 1996 R. A. Evarestov

It is a great pleasure to have this opportunity to thank Professor M. Car-

St. Petersburg, November 1992 R. A. Evarestov

2. Finite Groups and Their Representations ...................... 5

3. Symmetry Groups and Their Representations .................. 31

3.3.2 Symmetry of a Cyclic Model of a Crystal ............. 46

4. Site Symmetry and Induced Representations of Symmetry Groups 89

4.5.5 Space Groups and Crystal Structures

5. Application of Induced Representations in the Electron Theory

5.6.3 Energy Bands of AgBr from Cluster Calculations

6. Induced Representations in the Theory of Imperfect Crystals .... 185

7. Application of Induced Representations of Space Groups

8. Induced Representations of Space Groups

9. Site Symmetry in Magnetic Crystals

9.4 Induced Corepresentations of Magnetic Space Groups ..... 244

10. Site Symmetry in Permutation - Inversion Symmetry Groups

References .................................................... 269

Subject Index ................................................. 277

R. A. Evarestov et al., Site Symmetry in Crystals

ourselves somewhat and refer readers to [1.2,4,6]. Special attention is paid to

2.1 Elements of Group Theory

2.1.1 Groups. Generators and Generating Relations. Subgroups. Cosets.

This operation is called the composition law ("group multiplication", or

I g-lg = gg-l = E , g,g-l E G. (2.1.4)

R. A. Evarestov et al., Site Symmetry in Crystals

or for all gi E G . (2.1.8)

2.1.2 Conjugate Elements and Classes. Factorization of Groups

conjugation relation is reciprocal. This relation is also transitive. Two elements

elements of G (self-conjugate element) forms a class. For example, the identity

The product gigj of coset elements, which is an element of G, is a member of

The element h is labeled with indexes i andj because a given multiplier h E H is

If H is an invariant subgroup of G (H <J G) then G is called a semidirect

Finally, if both Hand Q are invariant subgroups of G then G is the direct

(gjhig j -I )h i-I E H , (2.1.20)

as well as to the group Q

g}higj-Ihi-I) E Q, Q<l G . (2.1.21)

A conjugacy class S(G) of the group G = H x Q consists of the elements

The number kG of classes in G is equal to the product of numbers of classes in

2.1.3 Homomorphism and Isomorphism of Groups

When a kernel N consists of a single element (the identity E) there is a

Isomorphic groups have the same order.

2.2 Elements of Group Representation Theory

2.2.1 Representations of a Group. Equivalent, Reducible

D(g)ei = L Dji(g)ej . (2.2.2)

An operator D(g) transforms a vector x with components Xi

in the space L into the vector x' also in the space L

x' == 15(g)x == ~ xi15(g)ei ==

1 15'(g) == 115(g)1-1 1 (2.2.7)

and the operator (2.2.7) has a matrix

D(g)em = L Dpm(g)ep . (2.2.10)

The space L of a reducible rep can be decomposed into a direct sum of

D(g) = L rp(i)(g) . (2.2.15)

D(g)S = SD(g) (2.2.16)

for all g EGis a zero matrix (B = 0).

The character of an element g E G in a rep D(g) is defined as the trace of the

x(g) = Tr{D(g)} = 'LDii(g) . (2.2.20)

x'(g) = Tr{D'(g)} = Tr{AD(g)A- 1} = Tr{D(g)} = X(g) (2.2.21)

2) All the elements of a conjugacy class have the same character:

= Tr {D(g)} = X(g) . (2.2.23)