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in Chemistry
“Talking of education, people have now adays’’ (said he) “got a strange opinion
that every thing should be taught by lectures. Now, I cannot see that lectures can
do so much good as reading the books from which the lectures are taken. I know
nothing that can be best taught by lectures. except where experiments are to be
shewn. You may teach chymestry by lectures  You might teach makmg of shoes
by lectures! ’’
J ames Boswell: Life of Samuel Johnson, 1766 (17091784)
“Every aspect of the world today  even politics and international relations  is
affected by chemistry”
Linus Pauling, Nobel Prize winner for Chemistry, 1954, and
Nobel Peace Prize, 1962
ABOUT THE AUTHOR
Mark Ladd hails from Porlock in Somerset, but subsequently, he and his
parents moved to Bridgwater, Somerset, where his initial education was at Dr
John Morgan’s School. He then worked for three years in the analytical
chemistry laboratories of the Royal Ordnance Factory at Bridgwater, and
afterwards served for three years in the Royal Army Ordnance Corps.
He read chemistry at London University, obtaining a BSc (Special) in
1952. He then worked for three years in the ceramic and refractories division
of the research laboratories of the General Electric Company in Wembley,
Middlesex. During that time he obtained an MSc from London University for
work in crystallography.
In 1955 he moved to Battersea Polytechnic as a lecturer, later named
Battersea College of Advanced Technology; and then to the University of
Surrey. He was awarded the degree of PhD from London University for
research in the crystallography of the triterpenoids, with particular reference
to the crystal and molecular structure of euphadienol. In 1979, he was
admitted to the degree of DSc in the Universeity of London for hs research
contributions in the areas of crystallography and solidstate chemistry.
Mark Ladd is the author, or coauthor, of many books: Analytical
Chemistry, Radiochemistry, Physical Chemistry, Direct Methods in
Crystallography, Structure Determination by Xray Crystallography (now
in its third edition), Structure and Bonding in Solidstate Chemistry,
Symmetry in Molecules and Crystals, and Chemical Bonding in Solids and
Fluids, the last three with Ellis Horwood Limited. His Introduction to
Physical Chemistry (Cambridge University Press) is now in its third edition.
He has published over one hundred research papers in crystallography and in
the energetics and solubility of ionic compounds, and he has recently retired
from his position as Reader in the Department of Chemistry at Surrey
University.
His other activities include music: he plays the viola and the double bass in
orchestral and chamber ensembles, and has performed the solo double bass
parts in the Serenata Notturna by Mozart and the Carnival of Animals by
SaintSaens. He has been an exhibitor, breeder and judge of Dobermanns,
and has trained Dobermanns in obedience. He has written the successful book
Dobermanns: An Owner s Companion, published by the Crowood Press
and, under licence, by Howell Book House, New York. Currently, he is
engaged, in conjunction with the Torch Trust, in the computer transcription
of Bibles into braille in several African languages, and has completed the
whole of the Chichewa (Malawi) Bible.
Mark Ladd is married with two sons, one is a Professor in the Department
of Chemical Engineering at the University of Florida in Gainsville, and the
other is the vicar of St Luke’s Anglican Church in Brickett Wood, St Albans.
He lives in Farnham, Surrey, with his wife and one Dobermann.
Symmetry and Group Theory
in Chemistry
Mark Ladd, DSc (Lond), FRSC, FInstP
Department of Chemistry
University of Surrey
Guildford
Foreword by
Professor the Lord Lewis, FRS
The Warden
Robinson College
Cambridge
Horwood Publishing
Chichester
First published in 1998 by
HORWOOD PUBLISHING LIMITED
International Publishers
Coll House, Westergate, Chichester, West Sussex, PO20 6QL
England
COPYRIGHT NOTICE
All Rights Reserved. No part of h s publication may be reproduced, stored in a
retrieval system, or transmitted, in any form or by any means, electronic,
mechanical, photocopying, recording, or otherwise, without the permission of
Horwood Publishing, International Publishers, Coll House, Westergate, Chichester,
West Sussex, England
0 M. Ladd, 1998
British Library Cataloguing in Publication Data
A catalogue record of this book is available from the British Library
ISBN 189856339X
Printed in Great Britain by Martins Printing Group, Bodmin, Cornwall
Table of contents
Foreword .................................................................................. ................. vVI
Preface ................................................................................................ ... vii
List of symbols ............................................................................................ . ~ i i  mi
. . . . .
1 Symmetry everywhere ...................................................................................... 1
1.1 Introduction: Looking for symmetry .............................................................. 1
................. 2
1.2 What do we mean by symmetry ..................................................................... 5
1.3 Symmetry throughout science ....................................................................... 6
1.4 How do we approach symmetry
Problems 1 .................................................................
1.1.1 Symmetry in finite bodies ...................................
1.1.2 Symmetry in extended patterns .................................................................. 4
2 Symmetry operations and symmetry elements ...............................
11
2.1 Introduction: The tools of symmetry
2.2 Defining symmetry operations, ele
.................... 11
...................... 13
....................................... 15 Sign of rotation ............................
2.2.4 Reflection symmetry .................
2.2.5 Rotoreflection symmetry.. ........
2.2.6 Inversion symmetry ................
2.2.8 Rotoinversion symmetry ........
....................................... 18
...................................... 19
2.5.1 Sum, difference and scalar (do
2.5.2 Vector (cross) product of two
2.5.3 Manipulating determinants and matrices .....................................
Orthogonality ............................... ..............................
2.5.4 Eigenvalues and eigenvectors.. ................................................................. .28
Diagonalization; Similarity transformation; Jacobi diagonalization ..... 303 1
Matrices and determinants; Cofactors; Addition and subtraction
of matrices; Multiplication of matrices; Inversion of matrices;
2.5.5 Blockdiagonal and other special matrices ....................................... 33
Adjoint and complex conjugate matrices;
matrix; Unitary matrix ......................................................................... 3435
........................................ 35
.................................. 38
.................................. 38
..................................... ..38
..................................
3 Group theory and point groups .............
3.1 Introduction: Groups and group the0
3.2 What is group theory .........................
3.2.1 Group postulates ............................................
3.2.2 General group definitions.. ..........................
3.2.3 Group multiplication tables .
3.2.5 Symmetry classes and conjugates ........
3.3.1 Deriving point groups.. ............................
3.3.2 Building up the
................................ 38
Inverse member ........... .................................... ................. 3839
Closure; Laws of co
.............................
................................
3.2.4 Subgroups and cos
3.3 Defining, deriving
...............................
................................... 46
............................ 52
......................... 59
Problems 3 ................................................................ ............................... 67
Euler's construction ...............................................
..........................................
4 Representations and character tables .........................................
4.1.1 Representations on position vectors .......................................
4.1 Introduction: What is a representation ............ ........................... 72
4.1.2 Representations on basis vectors ......................... ............................ 75
4.1.3 Representations on atom vectors.. ..... ............................................. 77
4.1.4 Representations on functions.. ............... ................................ 82
4.1.5 Representations on direct product functions .............................
4.2 A first look at character tables.. .................... .......................... 86
87 4.2.1 Orthonormality ............. ...........................................
4.2.2 Notation for irreducible representations ........ ............................. 88
89 Complex characters ......................................................................
4.3 The great orthogonality theorem ..................... ............................ 90
4.4 How to reduce a reducible representation ......................................... 94
4.5 Constructing a character table.. .......................... ................................ 96
4.6 How we have used the direct product .............. ............................ 103
Problems 4 ............................................................ ............................ 104
Unshiftedatom contributions to a re
5 Group theory and wavefunctions ........................... .............................. 108
108
................. 110
5.1 Introduction: Using the Schrodinger equation ...............................
5.2 Wavefunctions and the Hamiltonian operator.. .......................................... ,109
5.2.1 Properties of wavefunctions ................................
5.3.1 Defining operators in function space ....................................................... 112
5.5 When do integrals vanish ................................
5.3 A further excursion into function space.. ............................................
5.4 Using operators with direct products .........................................
5.6 Setting up symmetryadapted linear combinati
5.6.1 Deriving and using projection operators.. .....
5.6.2 Deriving symmetryadapted orbitals for the carbonate ion
5.6.3 Handling complex characters ...........................................
Problems 5 ................................................... ...................................... 128
115
............................... 117
............................... 119
Generating a second function for a degenerate representation
6 Group theory and chemical bonding ............................................................. 130
6.2 Setting up LCAO approximations.. ........................................................... .13 1
Function of the Schrijdinger equation ........
6.2.1 Defining overlap integrals.. .............................
6.1 Introduction: molecular orbitals .................................
Classlfylng molecular orbitals by symmetry ...............
....................................... 132
Introducing the variation principle .......
.............................. 134
6.2.2 Defining Coulomb and resonance inte .............................. 134
6.2.3 Applying the LCAO method to the oqgen molecule.. ............................ .137
6.2.4 Bonding and antibonding molecular orbitals and notation ....................... 140
........... 142
6.3 Pelectron approximations ...... .............................................................. 142
............................. 143
Benzene .................................................................................................. 144
6.3.2 Further features of the Huckel molecularorbital theory.. ........................ .149
llBond order ................................................ ........................ 149
Free valence .......................................................................................... .15 1
Charge distribution ................................................................ 152
..................................... 152
Methylenecyclobutene; methylenecyclopropene ...................................... 1 5 3
................. 156
Continuing with the variation principle ..............................
Total bond order ................................................
6.3.1 Using the Huckel molecular
6.3.3 Altemant and nonaltemant hydrocarbons .....
6 4 4 Huckel's 4n +2 rule ..........................................
6.3.4 Working with heteroatoms in the Huckel approximation157
Pyridine ...........................................................
6.3.5 More general applications of the LCAO appro
Pentafluoroantimonate(II1) ion ............................
First look at methane ............... ......................................................... 165
....................................... 169
....................................... 173
Sulfur hexafluoride. ................................... ............................... 178
.................. 186
6.4 Schemes for hybridization: water methane ............. ...... 167
6.4.1 Symmetrical hybrids ............................
Walsh diagrams ...................................
Further study of methane .....................
6.5 Photoelectron spectroscopy ..........................................................
6.6 Cyclization and correlation ....................
6.7.1 Electronic structure and term symbols ........................................
6.7 Group theory and transitionmetal compounds.. .......
RussellSaunders coupling.. .. ..................................................... 188
6.7.2 How energy levels are split in a crystal field.. .....
6.7.3 Correlation diagrams in 0, and Td symmetry ......................................... .197
6.7.4 Ligandfield theory .... ...................................................... ..... 205
Spectral properties ............................ ............................................... 211
Problems 6 .................................................................... ................... 217
.................... 192
Weak fields and strong fields ...............
'Holes' in d orbitals ..................................... ........................... 203
7 Group theory, molecular vibrations and electron transitions.. .................... .22 1
7.1 Introduction: How a molecule acquires vibrational energy.. .........
7.2 Normal modes of vibration ...................................
7.2.1 Symmetry ofthe normal modes ...................................................
7.3 Selection rules in vibrational spectra ................
7.3.1 Infrared spectra ......................................
Diatomic molecules ..................................................................
7.3.2 Raman spectra .............................................
7.4.1 Combination bands, overtone bands and Fermi resonance.. ..........
7.4.2 Using correlation tables withvibrational spectra ..................................... 239
7.4.3 Carbon &oxide as an example of a linear molecule ........................
7.5 Vibrations in gases and solids ....................................
7.6 Electron transitions in chemical species.. ..........................................
7.6.1 Electron spin.. ................................................................................
7.6.2 Electron transitions among degenerate states ......................................... .243
.............................. 222
................................... 230
Polarization of Raman spectra . . .............................................
7.4 Classlflmg vibrational modes ...................
...................... 241
7.6.3 Electron transitions in transitionmetal compounds,. ...................
Problems 7 ....... ..................................................................
8 Group theory and crystal symmetry ............................................................. 248
8.1 Introduction: two levels of crystal symmetry ...........
8.2 Crystal systems and crystal classes ...................
8.3 Why another symmetry notation ...................... ................................ .249
8.4 What is a lattice ........................................................................................ .2 5 2
8.4.1 Defining and choosing unit cells ............................ ................ 253
8.4.2 Why only fourteen Bravais lattices ......................................................... .256
8.4.3 Lattice rotational symmetry degrees are 1, 2, 3, 4 and 6 ....
8.5 Translation groups ......... ................. ............................... .263
8.6.1 Symmorphic space groups.. .................................................................... ,265
8.6.2 And nonsymmorphic space groups.. ...................................
.....................
8.4.4 Translation unit cells ......................................
8.4.5 WignerSeitz cells .............................................................
8.6 Space groups ........................................................................
................................ 261
Glide planes and screw axes .........................
Monoclinic nonsymmorphic space groups.. .......
Orthorhombic nonsymmorphic space groups .............................
Some useful rules; Tetragonal nonsymmorp
8.7 Applications of space groups ..........................
Naphthalene; Biphenyl; Two cubic structures
3 8.8 What is a factor group .................................
8.8.1 Simple factorgroup analysis of iron(I1) su
................................ 269
............ .272
............................... ,272
8.8.2 Sitegroup analysis.. ..................................... ...................... 284
Problems 8 ....................................................................................................... 285
Factorgroup method for potassium chro
Appendix 1 Stereoviews and models ................................................................. 288
Al .l Stereoviews ............................................................................................. 288
A1.2 Model with S, symmetry ......................................................................... 289
Appendix 2 Direction cosines and transformation of axes .................................. 291
A2.1 Direction cosines ..................................................................................... 291
A2.2 Transformation of axes ........................................................................... 292
Appendix 3 Stereographic projection and spherical trigonometry ....................... 294
A3.1 Stereograms ............................................................................................ 294
A3.2 Spherical triangles .................................................................................. 297
A3.2.1 Formulae for spherical triangles ........................................................... 297
A3.2.2 Polar spherical triangles ....................................................................... 298
A3.2.3 Example stereograms ........................................................................... 299
A3.2.4 Stereogram notation ............................................................................. 300
Appendix 4 Matrix diagonalization by Jacobi's method ...................................... 302
Appendix 5 Spherical polar coordinates ............................................................. 305
A5.1 Coordinates ............................................................................................. 305
A5.2 Volume element ...................................................................................... 305
A5.3 Laplacian operator305
Appendix 6 Unitary representations and orthonormal bases ............................... 307
A6.1 Deriving an unitary representation in C3" ................................................ 307
A6.2 Unitary representations from orthonormal bases ...................................... 310
Appendix 7 Gamma function ............................................................................. 312
Appendix 8 Overlap integrals ............................................................................ 313
Appendix 9 Calculating LCAO coefficients ....................................................... 314
Appendix 10 Hybrid orbitals in methane ............................................................ 316
Appendix 11 Character tables and correlation tables for point groups ................ 319
A1 1.1 Character tables . . .......................................................... .... 319
Groups C,, (n =1 oups C and C ; Groups S (n =4. 6).
Groups C (n =24); Groups C (n =26); Groups D (n =26);
Groups D (n =26); Groups D (n =24); Cubic Groups; Groups C and D ..
................. 337
Groups C (n =24, 6). Groups C (n =2
.................... 337
337
A11.2 Correlation tables ..............................................
Groups D , T and 0 ..............................
A1 1.3 Multiplication properties of irreducible r
General rules; Subscripts on A and B; Doublydegenerate
representations; Triplydegenerate representations; Linear
groups; Direct products of spin multiplicities .......................................
Appendix 12 Study Aids on the Internet ............................................................ 338
A12.1 Computer programs .............................................................................. 338
Programs 338
.........................................................................................................
Appendix 13 Some useful rotation matrices ....................................................... 342
Twofold symmetry; Threefold symmetry along <111>; .........................................
Threefold symmetry along [OO* 11; Fourfold symmetry;
Sixfold symmetry
Appendix 14 Apologia for a single symmetry notation ....................................... 345
Tutorial solutions ..................................................................................... .34 7394
References and selected reading ...................................................... .......... 3 953 97
Index
Foreword
by
Professor the Lord Lewis, FRS
Warden, Robinson College, Cambridge
There is an instant appeal and appreciation of symmetry within a system. The
recognition of symmetry is intuitive but is often difficult to express in any simple
and systematic manner. Group theory is a mathematical device to allow for the
analysis of symmetry in a variety of ways. This book presents a basic mathematical
approach to the expression and understanding of symmetry and its applications to a
variety of problems within the realms of chemistry and physics. The consideration
of the symmetry problems in crystals was one of the first applications in the area of
chemistry and physics, Hwdey observing in the mid19 century that “the best
example of hexagonal symmetry is furnished by crystals of snow”.
The general occurrence of symmetry is well illustrated in the first chapter of the
book. Its widespread application to a whole variety of human endeavour spreading
from the arts to sciences is a measure of the implicit feeling there is for symmetry
within the human psyche. Taking one speclfic example, let us consider
architecture, which is a discipline that is on the borderline between the arts and the
sciences and has many good examples of the widespread application of symmetry.
In the design and construction of buildings in general there is a basic appeal to
symmetry and this recognition was taken to a logical extreme in the archtecture of
the Egyptians. This applied particularly in the design of temples which were
constructed at one stage with the deliberate intention of introducing a lack of
symmetry; the So called “symmetrophobia”. This itself was a compelling point in
the visual form of the buildings and as such brought these buildings to the attention
of the public and placed them in a unique position compared to other forms of
architecture, consistent with their special function within the community.
The translation of symmetry consideration into mathematical terms and the
application to science has been of considerable use and has allowed for a generality
of approach to wide range of problems. This approach has certainly been of
importance in the study of inorganic chemistry’over the last four decades and is now
considered to be one of the main armaments in dealing with a wide range of
problems in this area; which cover as diverse a series of subjects as basic
spectroscopy, both electronic and vibrational, crystallography, and theoretical
chemistry with particular reference to the bonding properties in molecules. All
these areas are well covered and documented within the present text.
The prime aim of this book is to equip the practising chemist, particularly the
structural chemist, with the knowledge and the confidence to apply symmetry
arguments via the agency of group theory to solving problems in structural
chemistry. The use of symmetry within molecules to determine the structure of
molecules is not new to either the study of inorganic or organic chemistry.
Variation in the charge distribution within molecules was recognised as being
associated with the symmetry of the molecule and the use of techniques such as
xii Foreword
dipole moments or polarity within a molecule were readily associated with the
physical properties of compounds. A basic approach used by both in organic and
inorganic chemistry throughout the 19/20 centuries to the solution of a wide range
of problems involving the structure of molecules which depended on the symmetry
of the molecule was the use of isomer counting either as geometrical or optical
isomers. The final proof for the octahedral and planar arrangements of ligands
around a metal centre was the resolution of compounds of metals with these stereo
chemistries into optically active isomers. The present book develops this approach
giving it the added advantage of a mathematical rigor and applying the arguments
to a range of techniques involving symmetry with particular emphasis on using as
examples molecules that are familiar to the practising chemist.
The text allows the reader to develop the mathematical expertise necessary to apply
this approach. The availability of problem sets at the end of each chapter is
intended to build up the confidence to apply the procedure to examples outside the
text and is a very effective way of testing the mathematical appreciation of the
reader. It is, however, fair to say that the mathematical task set by the text will not
be easy for many students, but it is equally important to emphasise that the effort
that is involved will pay great dividends in the understanding of and application to
many aspects of chemistry. The author is to be congratulated on the clarity and
detail with which he deals with this basic mathematical ground work .
Another interesting feature of the present text is the introduction to computer
techniques for a number of the applications and in particular the use of the internet
for computer programs relevant to certain of the set problems, as well as the use of
stereoviews and models. This allows for a direct application to wide range of data
and is perhaps of particular importance in the area of theoretical chemistry .
In summary, is book provides the “enabling” background to rationalise and
synthesise the use of symmetry to problems in a wide range of chemical
applications, and is a necessary part of any modern course of Chemistry.
J Lewis
Robinson College
Cambridge
June 1998
PREFACE
This book discusses group theory in the context of molecular and crystal symmetry.
It stems from lecture courses given by the author over a number of years, and covers
both pointgroup and spacegroup symmetries, and their applications in chemistry.
Group theory has the power to draw together molecular and crystal symmetry,
which are treated sometimes from slightly Merent viewpoints.
The book is directed towards students meeting symmetry and group theory for the
first time, in the first or second year of a degree course in chemistry, or in a subject
wherein chemistry forms a sigdicant part.
The book presumes a knowledge of the mathematical manipulations appropriate to
an Alevel course in this subject: the vector and matrix methods that are used in the
book, that give an elegance and conciseness to the treatment, are introduced with
copious examples. Other mathematical topics are treated in appendices, so as not to
interrupt the flow of the text and to cater for those whose knowledge may already
extend to such material.
Computer power may be said to render some manipulations apparently
unnecessary: but it is very easy to use a sophisticated computer program and obtain
results without necessarily being cognizant of the procedures that are taking place;
the development of such programs, and even better ones, demands this knowledge.
Each chapter contains a set of problems that have been designed to give the reader
practice with the subject matter in various applications; detailed, tutorial solutions to
these problems are provided. In addition, there is a set of programs, outlined in
Appenhx 12, established on the Internet under the web address
www.horwood.net/publish that executes procedures discussed in the text, such as
Huckel molecularorbital calculations or pointgroup recognition. A general resume
of the programs is provided under the web address, but otherwise they are self
explanatory.
Symmetry is discussed in terms of both the Schonflies and the HermannMauguin
symmetry notations. The HermannMauguin notation is not introduced generally
until Chapter 8. By that stage, the concepts of symmetry and its applications will
have been discussed for molecules. Thus, the introduction of the second notation
will be largely on a basis of symmetry that will be, by then, well established and
understood.
A number of molecular and crystal structures is illustrated by stereoscopic
drawings, and instructions for viewing them, including the construction of a
stereoviewer, are provided.
The author has pleasure in expressing his thanks to Professor, The Lord Lewis,
Warden of Robinson College, Cambridge for helpful discussions at the beginning of
the work and for writing the Foreword; to Dr J ohn Burgess, Reader in Inorganic
Chemistry, University of Leicester for encouraging comments and for reading the
manuscript in proof; to various publishers for permission to reproduce those
diagrams that carry appropriate acknowledgements; and finally to Horwood
Publishmg Limited with whom it is a pleasure and privilege to work.
Mark Ladd, 1998
Farnham
List of symbols
The following list shows most of the symbols that are used herein. It is traditional
that a given symbol, such as k or j, has more than one common usage, but such
duplications have been kept to a minimum within the text.
A, B, .
A
A
A'
A+

A
A*
R
A?,
a
a
a
a,
av
0 0
B
b
b
b
C
crl
cn
C n
C
C
c,I
D
D
D*
De
Do
D n
d
d2
d
det(A)
Symmetry operations (operators) in a group
Spectroscopic term symbol
Irreducible representation; matrix; general constant; Aface centred unit
cell; member of a group
Matrix, inverse to A
Matrix, transpose of A
Matrix, adjoint to A
Matrix, conjugate to A
Cofactor matrix of A
ijth term of cofactor matrix R
Vector along the x axis
Molecularorbital energy level of symmetry type A
Constant of Morse equation; unitcell dimension along x axis; aglide plane
ith component of a vector a
ijth term of matrix A
Bohr radius for hydrogen (52.918 pm)
Irreducible representation; matrix; general constant; magnetic flux density;
B facecentred unit cell; member of a group
Vector along they axis
Molecularorbital energy level of symmetry type B
Unitcell dimension along y axis; 6glide plane
Cface centred unit cell; member of a group
Rotation symmetry operation (operator) of degree n
Rotation symmetry axis of degree n
Cyclic (point) group of degree n
Vector along the z axis
Unitcell dimension along z axis; cglide plane
LCAO coefficients (eigenvectors)
Debye unit (3.3356 x
Dmatrix; density
Dmatrix, conjugate to D
Dissociation energy (theoretical, including zeropoint energy)
Dissociation energy (experimental)
Dihedral (point) group of order n
d Orbital; d wavefunction; differential operator, as in  ; bond length
d2
Second differential operator, as in 
dx2
dGlide plane
Determinant, IAI, of matrix A
C m); spectroscopic term symbol
d
dx
List of symbols xv
E
E
E
E
el,
e
eV
F
F
€
f
f
A x )
G
6
g
H
H
H
ii
&
h
k
k
kB
L
1
Identity symmetry operation (operator)
Spectroscopic term symbol
Identity matrix; doublydegenerate irreducible representation; total energy;
Total electronic energy; electrical field strength
Unit vectors along mutually perpendicular directions i (i =1,2,3)
Doublydegenerate molecularorbital energy level of symmetry type E
Electronvolt (1.6022 x J)
Spectroscopic term symbol
Allface centred unit cell
Free valence
f Orbital; f wavefunction
function; force
function of a variable, x
Spectroscopic term symbol
Group, as in G{A, B, ..}
Order of subgroup; even (‘gerade’) function; Lande factor
Complete Hamiltonian operator
Nuclear Hamiltonilan operator; spectroscopic term symbol
Coulomb integral; magnetic field strength
Electronic Hamiltonian operator
Effective electronic Hamiltonian operator
Order of group; hybrid orbital; Hiickel parameter; Planck constant (6.6261
x
‘Crossh ’ (=h/27c)
Plane in a crystal or lattice
Form of planes (hkl)
Spectroscopic term symbol
Ionization energy; bodycentred unit cell
Transition moment (integral)
Unit vector along the x axis
Inversion symmetry operation (operator)
Centre of (inversion) symmetry
Infrared
Unit vector along they ax i s
Combined orbital (I) and spin (s) angular momenta for an electron
Total combined orbital (L) and spin (5‘) angular momenta for multielectron
Unit vector along the z axis
Number of symmetry classes in a point group; Hiickel parameter; force
Boltzmann constant (1.3807 x
Total orbital angular momentum
Orbital angular momentum quantum number; Miller index along z axis;
direction cosine along x axis
J HzI); Miller index along x axis
Ji
species
constant; Miller index along y axis
J K’)
xvi List of symbols
m,
m
N
N A
N
n
n

n
n
nP
0
0
P,
p,,
P
P
P
P
P
4
R
R
r
r

Rhex
Magnetization
Molar mass
Relative molar mass
CS
Minor determinant of qth term of matrix A
Reflection (mirror) plane symmetry operation (operator)
Reflection (mirror) plane symmetry; direction cosine along y axis
Mass of electron (9.1094 x lo” kg)
Quantum number for resolution of orbital angular momentum about the z
axis (‘magnetic’ quantum number)
Projection of s on the z axis (*%)
Magnetic moment
Normalization constant
Avogadro constant (6.0221 x mol’)
Number density
Rotation symmetry operation (operator) of degree n
Dimensionality of a representation; rotation symmetry axis of degree n;
c “ I
principal quantum number; number of atoms in a species; nglide plane;
direction cosine along z axis
Rotoinversion symmetry operation (operator) of degree n
Rotoinversion symmetry axis of degree n
Screw (rotation) axis (n =2, 3,4,6; p <n)
Operator; transformation operator
Octahedral (cubic) (point) group
Projection operator (operating on x)
Projection operator (operating on D(R)$
Position vector
Spectroscopic term symbol
Total bond order; primitive unit cell
p Orbital; p wavefunction
Mobile (p) bond order
Formal charge on an atom
General symmetry operation (operator)
Rhombohedra1 (primitive) unit cell; internuclear distance
Triplyprimitive hexagonal unit cell
Vector; unit bond vector
Length of vector r, that is, Irl; spherical polar (radial) coordinate; number
of irreducible representation in a point group; interatomic distance
Equilibrium interatomic distance
s Orbital; s wavefunction; spin quantum number (%) for single electron
Rotoreflection symmetry operation (operator) of degree n
Spectroscopic term symbol
Overlap integral; total spin for multielectron species
Rotoreflection symmetry axis (alternating axis) of degree n
Triplydegenerate irreducible representation
List of symbols xvii
T Tetrahedral (cubic) (point) group
t Translation vector
t
U
[ Direction in a lattice
<uvw>Form of directions [UVB'I
Triplydegenerate molecularorbital energy level of symmetry type T
Coordinate of lattice point along x axis
U
V
vm
\I
V
V
W
X
Xe
Y
Y
z
X
Z
a
aij
P
r
Y
A
6ij
5
e
&
K
h
CL
PI
PO
V
u

n
n*
P
n
Odd ('ungerade') function
Volume of a parallelepipedon; nuclear potential energy function (operator);
coordinate of lattice point along y axis; nuclear potential energy function
(operator)
Molar volume
Electronic potential energy function (operator)
Speed of light (2.9979 x 10' m s')
Vibrational quantum number
Coordinate of lattice point along z axis
General variable
Reference axis; fractional coordinate in unit cell
Anharmonicity constant
General variable
Reference axis; fractional coordinate in unit cell
Atomic number
Reference axis; fractional coordinate in unit cell
Interaxial angle y%; general angle; Coulomb integral H for a species with
itself; polarizability; electron spin (+%)
Components of 3 x 3 polarizability tensor
Interaxial angle zAx; general angle; Coulomb integral H between two
Representation; gamma hnction
Interaxial angle xAy; general angle
Triplydegenerate irreducible representation in C , and Dd ; ligandfield
Kronecker's delta
Complex exponential, as in exp(i2nln); vibrational energy
Magnetizability
General angle; spherical polar coordinate
Volume magnetic susceptibility
Eigenvalue; hybrid orbital constant
Dipole moment vector; reduced mass; spheroidal coordinate
Components of p (i =x, y, z)
Permeability of a vacuum (4n x 1 07 H m', or J C2 m s2 )
Frequency; spheroidal coordinate
Wavenumber
Doublydegenerate irreducible representation in C,, and D,h
n Bonding molecular orbital
n Antibonding molecular orbital
Electron density; exponent in atomic orbital (=2Zr/na, )
species; electron spin (95)
energysplitting parameter
xviii List of symbols
9*
9n
4'
X
Y
\v
v*
0
n
63
V2
Summation; irreducible representation in C,, or D,h
General reflexion symmetry operation (operator)
Reflexion symmetry operation (operator) perpendicular to principal C,, axis
Reflexion symmetry operation (operator) containing the principal C,, axis
General reflection symmetry plane; o bonding molecular orbital
(3 Antibonding molecular orbital
Reflexion symmetry plane perpendicular to principal C,, axis
Reflexion symmetry plane containing the principal C, axis
Volume (dz, infinitesimal volume element)
Quadruplydegenerate irreducible representation in C, and Dmh
Molecular orbital or wavefunction; spherical polar coordinate; spheroidal
Molecular orbital or wavefunction, conjugate to 0
Molecular orbital or wavefunction
LCAO molecular orbital
Trace, or character, of a matrix; mass magnetic susceptibility
Linear combination of wavefunctions v, total wavefunction
Atomic orbital or wavefunction
Atomic orbital or wavefunction, conjugate to yl
Angular frequency (=k/p)'
Hybrid orbital
Direct product
Laplacian operator
coordinate
1
Symmetry everywhere
Tyger! Tyger! burning bright
In the forests ofthe night,
What immortal hand or eye
Couldframe thy fearful symmetry?
William Blake (17571827): The Tyger!
1.1 INTRODUCTION: LOOKING FOR SYMMETRY
Generally, we have little difficulty in recognizing symmetry in twodimensional
objects such as the outline of a shield, a Maltese cross, a fivepetalled Tudor Rose,
or the Star of David. It is a rather different matter when our subject is a three
dimensional body. The difficulty stems partly from the fact that we can see
simultaneously all parts of a twodimensional object, and so appreciate the
relationship of the parts to the whole; it is not quite so easy with a threedimensional
entity. Secondly, while some threedimensional objects, such as flowers, pencils and
architectural columns, are simple enough for liS to visualize and to rotate in our
mind's eye, few of us have a natural gift for mentally perceiving and manipulating
more complex threedimensional objects, like models of the crystal of potassium
hydrogen bistrichloroacetate in Figure 1.1, or of the structure of pentaerythritol
Fig 1.1 Potassiumhydrogen bistrichloroacetate (CbC02)2HK
2 Symmetry Everywhere
[eh.l
Fig 1.2 Stereoview showing the packing of the molecules of pentaerythritol, C(CH20H)4, in
the solid state. Circles in order of increasing size represent H, C and 0 atoms; OB'O
hydrogen bonds are shown by double lines. The outline of the unit cell (q. v.) is shown, and
the crystal may be regarded as a regular stacking of these unit cells in three dimensions
shown in Figure 1.2. Nevertheless, the art of doing so can be developed with
suitable aids and practice. If, initially, you have problems with threedimensional
concepts, take heart. You are not alone and, like many before you, you will be
surprised at how swiftly the required facility can be acquired. Engineers, architects
and sculptors may be blessed with a native aptitude for visualization in three
dimensions, but they have learned to develop it, particularly by making and
handling models.
Standard practice reduces a threedimensional object to one or more two
dimensional drawings, such as projections and elevations: it is a cheap method, well
suited for illustrating books and less cumbersome than handling models. This
technique is still important, but to rely on it exclusively tends to delay the
acquisition of a threedimensional visualization facility. As well as models, we may
make use of stereoscopic image pairs, as with Figure 1.2; notes on the correct
viewing of such illustrations are given in Appendix 1. The power of the stereoscopic
view can be appreciated by covering one half of the figure; the threedimensional
depth of the image is then unavailable to the eye.
1.1.1 Symmetry in finite bodies
Four quite different objectsare illustrated in Figure 1.3. At first, there may not seem
to be any connection between a Dobermann bitch, a Grecian urn, a molecule of 3
chlorofluorobenzene and a crystal of potassium tetrathionate. Yet each is an
example of reflection symmetry: a (mirror) symmetryplane, symbol o (Ger. Spiegel
= mirror), can be imagined for each entity, dividing it into halves that are related as
an object is to its mirror image.
If it were possible to performphysicallythe operation of reflecting the halves of an
object across the symmetryplane dividing them, then the whole object would appear
unchanged after the operation. If we view the D o b e r m a ~ from the side its mirror
symmetrywould not be evident, although it is still present. If, however, we imagine
a reflecting plane now placed in front of the Dobermann, then the object and her
image together would showc symmetry, across the plane between the object animal
and its mirror image (Figure 1.4). This plane together with that through the
Sec 1.1] Introduction: Looking for Symmetry 3
Doberrnann, and her mirror image, combine to give another symmetry element ,
along the line of intersection of the two symmetry planes. We shall consider later
the combinations of symmetry elements.
Often, the apparent symmetry of an object may not be exact, as we see if we
pursue the illustrations in Figure 1.3 a little further . The Doberrnann, beautiful
animal that she is, if scrutinized carefully will be seen not to have perfect c
symmetry; again, only the outline of the urn conforms to mirror symmetry. In a
molecule, the atoms may vibrate anisotropically, that is, with differing amplitudes of
vibration in different directions ; this anisotropy could perturb the exact c symmetry
depicted by the molecular model.
Under a microscope, even the most perfectlooking real crystals can be seen to
have minute flaws that are not in accord with the symmetry of the conceptually
F
iTo
110
001
100
I
I
I 110
110
 100
Fig.I.3 Examples of reflection symmetry: (a) The Dobennann, Vijentor Seal of Approval at
Valmara (c vertical ); (b) Grecian urn (o vertical) ; (c) 3Chloroflurobenzene molecule (c in
the molecular plane) ; (d) Crystal of potassium tetrathionate; o vertical , relating faces with
Miller indices!l) (hkl) and (h k l) .
4 Symmetry Everywhere [Ch. I
Fig 1.4 Vijentor Seal of Approval at Valmara: object and mirror image relationship across a
vertical (J symmetry plane . From a threedimensional point of view, there are three symmetry
elements here: the (J plane just discussed, the (J plane shown by Figure 1.3a, and an element
arising from their intersection. What is that symmetry element?
perfect crystals shown by drawings such as Figures 1.1 and 1.3d. Then, if we
consider internal symmetry, common alum KAI(S04h.12 H
20,
for example, which
crystallizes as octahedra, has an internal symmetry that is of a lesser degreee than
that of an octahedron.
1.1.2 Symmetry in extended patterns
If we seek examples of symmetry around us, we soon encounter It III repeating
patterns, as well as in finite bodies. Consider the tiled floor or the brick wall
illustrated by Figure 1.5. Examine such structures at your leisure, but do not be too
critical about the stains on a few of the tiles, or the chip off the occasional brick.
Geometrically perfect tiled floors and brick walls are, like perfect molecules and
crystals, conceptual.
Each of the patterns in Figure 1.5 contains a motif, a tile or a brick, and a
mechanism for repeating it in a regular manner. Ideally, the symmetry of repetition
implies infinite extent , because the indistinguishability of the object before and after
a symmetry operation is the prime requirement of symmetry. The stacking of bricks
(a) (b)
Fig 1.5 Symmetry in patterns: (a) plan view of a tiled floor; (b) face of a brick wall .
to form a brick wall is limited by the terminations of the building of which the wall
is a part , just as the stacking of the unit cells of a crystal is limited by its faces . In
Sec 1.2] What do we mean by Symmetry? 5
both examples, we may utilize satisfactorily the symmetry rules appropriate to
infinite patterns provided that size of the object under examination is very large
compared to the size of the repeating unit itself.
Real molecules and chemical structures, then, rarely have the perfection ascribed
to them by the geometrical illustrations to which we are accustomed. Nevertheless,
we shall find it both important and rewarding to apply symmetry principles to them
as though they were perfect, and so build up a symmetry description of both finite
bodies and infinite patterns in terms of a small number of symmetry concepts.
1.2 WHAT DO WE MEAN BY SYMMETRY?
Symmetry is not an absolute property of a body that exhibits it; the result of a test
for symmetry may depend upon the nature of the examining probe used. For
example, the crystal structure of metallic chromium may be represented by the body
centred cubic unit cell shown in Figure 1.6a, as derived from an Xray diffraction
analysis of the the crystal: the atom at the centre of the unit cell is, to Xrays,
identical to those at the corners, and there are two atoms per unit cell. Chromium
has the electronic configuration (lS)2 (2S)2 (Zp)" (3S)2 (3p)6 (3d)5 (4S)I, and the
unpaired electrons in this species are responsible for its paramagnetic property. If a
crystal of chromium is examined by neutron diffraction, the same positions are
found for the atoms. However, the direction of the magnetic moment of the atom at
the centre of the unit cell is opposite to that of the atoms at the corners (Figure
1.6b). Xrays are diffracted by the electronic structure of atoms, but neutron
diffraction arises both by scattering from the atomic nuclei and by magnetic
interactions between the neutrons and the unpaired electrons of the atoms. The
magnetic structure of chromium is based on a primitive (pseudobodycentred) cubic
unit cell, so it is evident that symmetry under examination by neutrons can differ
from that under examination by Xrays.
In this book, we shall take as a practical definition of symmetry that property ofa
body (or pattern) by which the body (or pattern) can be brought from an initial
spatial position to another, indistinguishable position by means of a certain
operation, known as a symmetry operation. These operations and the results of their
actions on chemical species form the essential subject matter of this book.
Fig. 1.6 Unit cell and environs of the crystal structure of metallic chromium: (a) from Xray
diffraction, (b) from neutron diffraction. The arrows represent the directions of the magnetic
moments associated with the unpaired electrons in the atoms.
6 Symmetry Everywhere [Ch.I
1.3 SYMMETRY THROUGHOUT SCIENCE
The manifestations of symmetry can be observed in many areas of science and,
indeed, throughout nature; they are not confined to the study of molecules and
crystals. In botany, for example, the symmetry inherent in the structures of flowers
and reproductive systems is used as a means of classifying plants, and so plays a
fundamental role in plant taxonomy. In chemistry, symmetry is encountered in
studying individual atoms, molecules and crystals. Curiously, however, although
crystals exhibit only nfold symmetry (n = 1, 2, 3, 4, 6), molecules (and flowers),
with fivefold or sevenfold symmetry are well known. The reasons for the limitations
on symmetry in crystals will emerge when we study this topic in a later chapter.
Symmetry arises also in mathematics and physics. Consider the equation
r = 16. (1.1)
The roots of (1.1) are X = ±2 and X = ±2i, and we can see immediately that these
solutions have a symmetrical distribution about zero. The differential equation
d
2Y1dX2
+k'Y = 0 (1.2)
where k is a constant, represents a type encountered in the solution of the
Schrodinger equation for the hydrogen atom, or of the equation for the harmonic
oscillator. The general solution for (1.2) may be written as
Y = A exp(ikX) + B exp(ikX) (1.3)
where A and B also are constants. If we consider a reflection symmetry that converts
X into X, then the solution of (1.2) would become
Y=A exp(ikX) +B exp(ikX) (1.4)
Differentiating (1.4) twice with respect to X shows that this equation also is a
solution of (1.2). If, instead of reflection symmetry, we apply to (1.3) a translational
symmetry that converts X into X + t, where t is a constant, we would find that
although the imposed symmetry has translated the function (1.3) along the x axis,
the applicability of the general solution remains.
A singlevalued, continuous, onedimensional, periodic function defined, for
example, between the limits X = ±Y2, can be represented by a series of sine and
cosine terms known as a Fourier series:
y
h=oo
A
o
+ 2 LA
h
cos (2rrhX) + B
h
sin(2rrhX),
h=l
(1.5)
where A
o
is a constant. A typical cosine term, as in Figure 1.7, shows symmetric
behaviour (Y
c
= Y
c
) with respect to the origin: it is equivalent to a reflection of the
curve across the line X = 0, and is an exemplar of an even function.
In contrast, a typical sine term, illustrated by Figure 1.8, is termed an odd
function, as it is antisymmetric (y_. = Y.) about the origin; the curve is mapped on
to itself by a rotation of 180
0
(twofold rotation) about the pointX= Y= O.
Sec 1.3]
 ~
Symmetry throughout Science
y axis
7
Fig. 1.7 Curve of cos(27thx): h = 2; \I, S x S +\1,. Reflection of the curve across the line x = 0
leaves the curve indistinguishable from its initial state; the function is even.
y axis
y,
Fig. 1.8 Curve of sin(27thx): h = 2; \I, S x S +Y.. Rotation of the curve about the point x = y
= 0 by 180
0
leaves the curve indistinguishable from its initial state; the function is odd.
EXAMPLE 1.1. Isj(x) = [x
3
cos(x)  x] an even or an odd function?
We need to evaluate the function at a few point around zero:
X
0.2
0.1
3
[X cos (X)  Xl
0.192
0.099
3
X
[X c cs t x )  Xl
0.2 0.192
0.1 0.099
0 Zero
Evidently, the functionj(x) is odd.
EXAMPLE 1.2. The electron density p(x) in Rutile, Ti0
2
, projected along the x axis, can be
expressed by the Fourier series (1.5). We use the Xray crystallographic data below to
8 Symmetry Everywhere [eh.l
compute p(x), conveniently at intervals of 1/32, from 0/32 to 8/32 only: the function is even,
and is reflected across the lines at x =1/4, 1/2 and 3/4.
o
18.0
2
3.9
4
7.3
6
5.9
8
0.5
10
3.0
12
1.0
Bi; is zero for all values of h observed experimentally because of the synunetry of the
structure. Forming the sum, we obtain
x
p(x)
o
61.2
1
36.3
2
9.9
3
6.7
4
2.4
5
11.5
6
24.1
7
17.5
8
10.0
The function may be plotted and extended to 1/2, 3/4, or the complete repeat period of unity.
The titanium atoms, represented by the highest peak, lie at x = 0, 1/2 and 1 (equivalent to 0
by translation), and the oxygen atoms at x, (\I,  x), (\I, + x) and (1  x), where x, from the
graph, is 0.19. Ideal line peak profiles for the atomic positions would be obtained only with a
very large nurnber'" ofAll data.
Finally here, we consider the framework of a cube constructed from twelve identical
I ohm resistors, as shown in Figure 1.9. Let an electrical circuit include the path
through the points A and G, which lie on a (threefold) symmetry axis of the cube.
The planes ACGE, ADGF and ABGH are all rr planes, of the type that we have
already discussed. We can use the symmetry properties of the cube to determine the
effective resistance of the cube to a current I flowing along a path from A to G. The
symmetry equivalence of the three paths emanating from A and of the three paths
converging at G requires that the currents in AB, AD, AE, CG, FG and HG are all
equal to 1/3, flowing in the directions shown by the arrows. The c symmetry
requires that the currents in EF and EH are the same, so that each is equal to 1/6; it
follows that the currents through BF and DH are also equal to 1/6. A similar
argument applies to the paths BC and DC. Thus, the effective resistance of the cube
for a path from A to G is 1/3 + 1/6 + 1/3, or 5/6, ohm.
Fig. 1.9 Framework of a cube formed by twelve identical 1 ohm resistors; the current I flows
through the network from A to G
Problems 9
1.4 HOW DO WE APPROACH SYMMETRY
Symmetry, then, is a feature of both scientific and everyday life[26
1.
In the following
chapters, we shall study the symmetry of chemical species and the applications of
symmetry principles in chemistry. However, before embarking on these topics, we
shall have to spend some time sharpening our notions of molecular symmetry, and
in acquiring the requisite descriptive and manipulative tools.
We have seen that symmetry may be made manifest through both geometrical
drawings and mathematical equations. The choice of approach is dictated largely by
the application under consideration. On the one hand, when we are considering
symmetry in relation to chemical bonding or molecular vibrations, the techniques
that evolve through group theory are the more appropriate. On the other hand, in
the study of crystals and crystal structure it may be enlightening sometimes to use a
more illustrative procedure. Some topics, such as the derivation of point groups, can
be studied readily by both methods: we shall try to make the best choice for each
application.
PROBLEMS 1
1.1 What symmetry is common to the following twodimensional figures: (a) the
emblem of the National Westminster Bank pic, (b) the emblem of the Mercedes
Benz car, and (c) the molecular skeleton of cyanuric triazide (1,3,5
triazidotriazine)? Is there any other symmetry present in any of these objects?
a
b c
1.2 Find the following objects in the home, or elsewhere, and study their symmetry.
Report the numbers and nature of the o planes and symmetry axes present.
(a) Plain cup;
(b) Rectangular plain table;
(c) Plain glass tumbler;
(d) Inner tray of matchbox;
(e) Round pencil, sharpened conically;
(f) Plain brick, with plane faces;
(g) Round pencil, unsharpened;
(h) Gaming die;
(i) Chair;
(j) Single primrose floret.
1.3 Study the patterns of the tiled floor and brick wall shown by Figures 1.5a and
1.5b. Illustrate each pattern by a number (preferably a minimum) of points
neccessary to represent it, where each such point has a constant location in the
pattern motif, such as its top, lefthand comer. Indicate relative dimensions, as
appropriate.
10 Symmetry Everywhere [eh.l
1.4 Twelve 1 ohm resistors are connected so as to form the outline of a regular
octahedron, which has the same symmetry as a cube. An electric circuit is
completed across a pair of opposite apices of the octahedron. Use the symmetry of
the octahedron to determine the effective resistance of a path through the octahedral
network.
1.5 State the even or odd nature of the symmetry of the following functions of a
variable X: (a)xB; (b) sin
2(X);
(c) (I/X) sin(X); (d)Xcos
2(X);
(e)Xtan(X).
1.6 Write in upper case those letters of the alphabet that cannot exhibit symmetry.
The letters should be treated as twodimensional, and your answer could depend
upon how you form the letters.
2
Symmetry operations and symmetry elements
Our torments also may in length of time
Become our elements.
J ohn Milton (16081674): Paradise Lost
2.1 INTRODUCTION: THE TOOLS OF SYMMETRY
In order that the concept of symmetry shall be generally useful, it is necessary to
develop precisely the tools of symmetry, the symmetry operations and symmetry
elements appropriate to finite bodies which, for our purposes, are mainly chemical
molecules. Then, as a prerequisite to group theory and its applications to chemistry,
we shall consider some of the basic manipulations of vectors and matrices that can
be used to simpllfy the discussion of symmetry operations and their combinations.
There exist two important notations for symmetry, and both of them are in general
use. In studying the symmetry of molecules and the applications of group theory in
chemistry, we shall make use of the Schonilies notation, as is customary. When we
come to consider the symmetry of the extended patterns of atomic arrangements in
crystals, the HermannMauguin notation is always to be preferred. Once we have
become familiar with symmetry concepts in the first of these notations, the
HermannMauguin notation will produce little difficulty.
2.2 DEFINING SYMMETRY OPERATIONS, ELEMENTS AND
We follow our statement of symmetry in Section 1.2, and define a symmetry
operation as an action that moves a body into a position that is indistinguishable
fiom its initial position: it is the action of a symmetry operation that reveals the
symmetry inherent in a body. A symmetry operation may be considered to take place
with respect to a symmetry element. A symmetry element is a geometrical entity, a
plane, a line or a point, which is associated with its corresponding symmetry
operation. It is preferable not to say that a symmetry element generates symmetry
operations in a body: a body may or may not possess symmetry; if symmetry is
present, that symmetry is revealed through a symmetry operation, and with that
operation we may associate the corresponding symmetry element.
OPERATORS
2.2.1 Operators and their properties
An operator is, in general, the symbol for an operation that changes one function
into another. Thus, if we write
0 ( h 2 +x ) =4 x + 1, (2.1)
12 Symmetry operations and symmetry elements [Ch. 2
0 is an operator acting on the function 2x2 +x; in this example it is the differential
operator ( ). There are many such operators and a particular case is that of the
d
linear operator. An operator 0 is linear if, for any functionJ
Okf= k(OJ),
o(ri +h 1 =of; +Of,
where k is a constant, and if
d
dx
wheref; andh are two functions. Evidently,  ( ) is a linear operator but In( ), for
example, is not. Linear operators possess several important properties, as follow:
The sum of two linear operators O1 and O2 acting on a given functionfis given by
(2.4) (01 +0 2 Y= Od + 0 2 f ;
the parenthetical expresion may be calculated first, if appropriate.
The product of two linear operators follows the rule
010f= OI(O2J). (2. 5)
01 ( 0 2 +0 3 ) =0 1 0 2 +0 1 0 3 , (2.6)
01 ( 0 2 0 3 ) =(oioz)03. (2.7)
Linear operators follow the distributive law
and the associative law,
d d’
br dx
EXAMPLE2.1. LetOI = ( ) , 0 2 = x 2 ( ) , 0 3 = ?( ),04=2( ) , k=2, f i =X 3 k+ 1,
fi =2.x’  3. Then, from the foregoing:
(a) ~ f i =3x2  2;
(c) 0 1 cfi +f2 ) =of; +O h =(3x2  2) +(4x) =3x2 +4x  2;
(b) 0 1 kfi =k(O& =k(3x2  2) =6x2  4;
(d) (01 +03s =Of; +Oji =( 3x 2  2) +6~=3x2 +6~ 2;
(e) 010ji =01(02fi) =01(xs  2x3 +x z) =5x4  6xz +2x.
Note that
0 2 0 f ; =0 2 (Of; ) =0 2 (3x2  2) =3x4  2x2 f OlOji
but
0104 =01(04) =01(Zu’  4~ +2 ) =6 x 2  4 =040fi.
Except for special cases two operators do not commute, that is,
oio, f o,o,. (2.8)
2.2.2 Symmetry elements
In Figure 2.1 we may imagine a symmetry element which is an axis of fourfold
rotational symmetry normal to the square (a), passing through its centre; we
Sec. 2.21 Defining Symmetry Operations 13
(a)
symbolize this element as C4. The italic letters on the figure are used to monitor the
motion of the square about the axis, and should not be regarded as a part of it. The
operator C4 determines the operation, also symbolized by C4 , that is carried out. In
words, C4 (square) =‘square rotated anticlockwise by 90’ about the symmetry
element C4 ’ .
Strictly, symmetry elements are conceptual, but it is convenient to accord them a
sense of reality, and they may be considered to connect all parts of a body into a
number of symmetrically related sets. Frequently, different symmetry operations
correspond to one and the same symmetry element. We identifl the combination of
the two operations (a) to (c) in Figure 2.1 as Ca and, similarly, (a) to (d) may be
written C: . Thus, we may regard Cf and C: as either multiplestep operations of
C4 or singlestep operations in their own right: but all are contained within the
symmetry of the square, and are associated with the single symmetry element C4.
2.2.3 Rotation symmetry
We consider next the individual symmetry elements of finite bodes, specifically
molecules, and firstly the rotation axis. We have used this symmetry element in the
discussion of Figure 2.1, and we define it now formally. A molecule is said to
a b
d
T c4
d a
c4

C
C b
b C
a
C d
b a
Fig. 2.1 Illustration of fourfold rotational symmetry: the C4 rotation axis is normal to the
square and passes through its centre; the symbol at the centre represents the C4 axis.
Successive C4 operations move the square through the sequence (a) +(b) +(c) +(d) +
(a)+(b) ... .
exhibit an nfold rotational symmetry axis, symbol C,,, if a rotation of (36Oh)O about
that axis brings the molecule into an orientation indistinguishable from that before
14 Symmetry operations and symmetry elements [Ch. 2
exhibit an nfold rotational symmetry axis, symbol C,, if a rotation of (36Oh)O about
that axis brings the molecule into an orientation indistinguishable from that before
the operation. Weuse now the word ‘orientation’ instead of the more general term
‘position’ because, as weshall see, no symmetry operation on a finite body produces
any translational motion of that body.
In principle, the value of n can range from unity to infinity, and several different
values are found for molecules. Figure 2.2 shows the fivefold symmetry of
nitrosylcyclopentadienylnickel. The value of infinity for n is found in linear
molecules; thus, iodine monochloride, IC1, has a C, axis along the length of the
molecule.
1 I
Fig 2.2 Stereoscopic illustration of the molecule of nitrosylcyclopentadienylnickel,
(CsH5)NONi. The vertical axis is C5, and there are five vertical cr planes, each passing
through the Ni, N and 0 atoms and one >CH group.
I
I
I
I
I
I
I
I
I
I
I
Fig. 2.3 Cube, showing a (vertical) Cdaxis along which the cube may be imagined to be
compressed to a square.
In two dimensions, the rotation axis, strictly, collapses to a poinf of rotation.
Imagine compressing a cube in a direction normal to a face until it becomes a
square. The C4 axis along the direction of compression, Figure 2.3, would become a
point at the centre of the square, as in Figure 2.1. However, weretain the notation
C, in twodimensional symmetry elements; they are, after all, conceptual.
Sec 2.21 Defining Symmetry Operations 15
Sign of rotation
We distinguish between clockwise and anticlockwise rotations in the following
manner: the fourfold rotation operation, for example, illustrated by Figure 2.1, is
symbolized as C4 (sometimes C 4‘ ) for an anticlockwise rotation of the object or of a
vector within it, and C i1 (sometimes C 4 ), the inverse of C4, for the corresponding
clockwise movement. Thus, in the given example, the positional result of C: is
equivalent to that of C i1 . Wemay note en passant that the convention adopted here
for rotation is the same as that used for the sign of an angular momentum vector
resolved along the z reference ax i s in a species.
2.2.4 Reflection symmetry
A reflection symmetry plane, symbol o, is said to be present in a molecule If it
divides that molecule into halves that are related to each other as an object is to its
mirror image. The operation of reflection, unlike rotation, cannot be performed
physically on a body, but if it could, the body would be indistinguishable before and
after the reflection. In combination with a rotation axis, it is necessary to distingwsh
between a reflection plane normal to the rotation axis, o h (h =horizontal), and one
containing that axis, o,(v =vertical). In Figure 2.2, five o, planes are present: each
contains the vertical C, axis, and passes through a >CH group, the centre of the
opposite C 4 bond, and the Ni, N and 0 atoms.
In two dimensions, reflection may be said to take place across a line: it remains
symbolized as o, but the subscripts ‘h’ and ‘v’ become superfluous. Thus, in Figure
2.1 we could draw four CY reflection lines, all passing through the centre of the
square. We may note that a reflection line will result from projecting a three
dimensional figure, with a o symmetry plane, on to a plane that is normal to the o
plane in the object. The reader is invited to draw a projection of the
nitrosylcyclopentadienyl molecule in the plane of the cyclopentadienyl ring, and to
mark in the o lines.
2.2.5 Rotoreflection symmetry
A molecule contains an nfold rotoreflection axis (also called an alternating axi s),
symbol S,,, if it is brought into an orientation indistinguishable from its original
orientation by means of a rotation of (36Oh)O about that axi s, followed by reflection
across a plane normal to the axis, the two movements constituting a single
symmetry operation. It is important to note that the ‘reflection ’plane used here may
not be a symmetry (reflection) plane of the molecule itselJ For example, Figure 2.4
is a stereoview of the dihydrogenphosphate ion, IH,P04], which exhibits the
symmetry element S4, but does not, itself, possess reflection symmetry. However, in
the tetracyanonickelate(I1) ion, Ni[CN4]*, Figure 2.5, the S4 axis is normal to a (3
plane, the plane of the ion itself.
16 Symmetry operations and symmetry elements
[Ch. 2
Fig. 2.4 Stereoscopic illustration of the dihydrogenphosphate ion, [H2PO4], as in crystalline
potassium dihydrogen phosphate; circles in order of increasing size represent H, 0 and P
atoms. Two of the four hydrogen atom sites on each ion are occupied in a statistical manner
throughout the structure: we may regard the sites as occupied by four halfhydrogen atoms
per ion. The only symmetry element here is S4, normal to the plane of the drawing.
A
Fig.2.5 Stereoscopic diagram of the tetracyanonickelate(II) ion, Ni[CN4I2; circles in order of
increasing size represent C, N and Ni atoms. The axis normal to the drawing is C4, with S4
collinear. The molecular plane is bh and the centre of the molecule is an inversion centre, i.
The combined actions of the S, and o h symmetry elements result in a C4 axis
coincident with S4: but the important point here is that the plane involved in the S4
operation is now also a symmetry plane of the species.
In general, we note that for a finite body containing an S, axis but no other
symmetry element, a 0 reflection plane does not coexist as a symmetry element
within that body i f n is an even number. An equivalent element to S1 is a (J plane
normal to the direction of Sl .
2.2.6 Inversion symmetry
The inversion operation i acts through a point in a molecule, its centre of symmetry,
and consists in taking every part of the molecule in a straight line through that point
to an equal distance on the opposite side of it: it results in an inversion of its
configuration. The species illustrated by Figure 2.5 contains the element i , as does
Sec. 2.21 Defining Symmetry Operations 17
the molecule of dibenzyl, Figure 2.6. The operation i is equivalent to S2, but the
former designation is preferred for this symmetry operation. In two dimensions i
degrades to a twofold rotation operation about a point.
We may choose to arrange all symmetry operations of molecules under two
headings, proper rotations C, and improper rotations S,. However, it is
conventional to use both elements (J and I , rather than S, and S,, respectively, in
discussing molecular symmetry.
2.2.7 Identity symmetry
The identity operation, symbol E (Ger. Einheit =unity), consists effectively in doing
nothing to the object. Alternatively, we may regard it as a C1 rotation about any axis
(C,) through a body. All molecules possess identity symmetry; some, such as
CHFClBr, Figure 2.7, show no other symmetry. The E operation, although
apparently trivial, is fundamental to group theory. With reference to Figure 2.1,
C , and C in general, is equivalent to identity.
2.2.8 Rotoinversion symmetry
The rotoinversion axis is not a part of the Schonflies notation, but we describe it
Fig. 2.6 Stereoscopic illustration of the structure of the molecule of dibenzyl, (C&IsCH2)2;
circles in order of increasing size represent H and C atoms. An inversion centre lies halfway
along the central CC bond.
Fig 2.7 Stereoscopic illustration of the molecule of fluorochlorobromomethane, CHFCBr,
an example of identity symmetry; circles in order of increasing size represent H, C, F, C1and
Br atoms.
18 Symmetry operations and symmetry elements [Ch. 2
here as it will be needed when we consider crystal symmetry within the Hermann
Mauguin symmetry notation. Like the rotoreflection axis, it is a single symmetry
operation consisting of two movements, a rotation of (36O/n)O about the ;axis
followed by inversion (Section 2.2.6) through a point on the i axis; this point is a
centre of symmetry only when i is an odd integer. Figure 2.4 shows the symmetry
element 4 : evidently, it is equivalent to the symmetry element S4, but the operation
4 is equivalent to the operation S i , with the same sense of rotation in each case.
An equivalence between S, and ;is not general. We note also that the point of
inversion on the ; axis is also the origin of the reference axes (see Section 2.3), for
reasons that we discuss in Section 3.3.
To facilitate an understanding of the symmetry operation S4 (and i), instructions
are given in Appendix 1 for constructing a model that possesses this symmetry. As
we may show from the next chapter, for a body that has a single symmetry element
S, , the following relationships hold for the corresponding operation (n 2 1).

For n odd: S, =Combination of C, and Oh;
For n even: S4n2 =Combination of CZn, and i;
S4n No equivalence
It is sometimes stated that S4 is equivalent to the combination of C4 and Oh. While
this statement provides a way of looking at the symmetry operation S4, it is implicit
then that the body in question possesses also the symmetry element (3h and so
contains a symmetry operation higher than S4 (see also Section 2.2.5 and Problem
3.6). Further discussions on symmmetry may be found in ~tandard”’~’ literature .
2.3 SETTING UP REFERENCE AXES
It is convenient to discuss molecules and their symmetry by reference to right
handed axes that are mutually perpendicular (Figure 2.8); such axes are termed
orthogonal (see also Section 4.2. l ), and the sequence x +y +z simulates a right
handed screw movement.
The selection of the orientation of reference axes within a molecule is somewhat
arbitrary: the molecule knows nothing about the axes we have set up in Figure 2.8.
We shall adopt a convention that is common, albeit not universal. The z reference
ax i s is aligned with the principal axis, that is, the rotation axis of highest degree : if
there are two or more axes of that degree, z is chosen so as to intersect the
maximum number of atoms. If the molecule is planar and z lies in that plane, the x
axis lies normal to the plane, that is, the molecular plane is the yz plane. If the
molecule is planar and z is normal to that plane, then y lies in the plane and,
preferably, passes through the maximum number of atoms. In each case the x axis is
perpendicular to both y and z, as in Figure 2.8.
Sec 2.41
A
zaxis
yaxis
Relationship of Symmetry to Chirality
Fig. 2.8 Orthogonal reference axes: f l y =y"z =z"x =90"
19
Fig 2.9 Stereoview of the transtetranitrodiamminocobaltate@) ion, [Co(NO2)4(NH2)2];
circles in order of increasing size represent N, 0, N H 2 and Co species. The N H2 groups are in
free rotation, and their effective shape is spherical.
A molecule may exhibit symmetry axes of more than one degree. Figure 2.9
illustrates the transtetranitrodiamminocobaltate(II1) ion, which shows both C4 and
C, symmetry axes: the principal axis is C4, and z is aligned with this axis. How
would the x and y axes be set for this molecule? Wemay note that when the axes are
not orthogonal, the usual notation for the interaxial angles is y^z = a, zAx =p and
xAy =y. Any other orientation of the orthogonal axes could have been made, but a
common sense choice leads normally to the simplest manipulations.
2.4 RELATIONSHIP OF SYMMETRY TO CHIRALITY IN MOLECULES
We noted in Section 2.2.6 that all symmetry operations with which we are
concerned here are either proper rotations C, or improper rotations S,.. Chiral
molecules, that is, those with one asymmetric centre or more, such as lactic acid
CH3C*H(OH)C02H, exhibit optical activity: they rotate the plane of polarization of
planepolarized light. The necessary and saci ent condition for a molecule to be
optically active is that it cannot be superimposed on to its mirror image. When this
condition holds, the molecule exists in two forms known as enantiomers.
Superimposability depends upon symmetry. A molecule with an S, axis is always
superimposable on to its mirror image, as the following argument shows.
20 Symmetry operations and symmetry elements [Ch. 2
Whatever the orientation of a given molecule it can have only one mirror image. If
the molecule possesses an S,, axis we may choose, arbitrarily, that the image plane
coincides with the reflecting plane associated with the S,, symmetry element. From
the discussions in Sections 2.2.5 and 2.2.8, if n is an odd integer, then the reflecting
plane exists as a symmetry element, and the molecule is superimposable on to its
mirror image. If n is even and q, does not exist in the molecule, then the operation
S, does not lead immediately to a superimposable mirror image. However, if the
whole molecule is then rotated by ( 36O/ n) O, the molecule and its mirror image are
superimposable. An alternative way of looking at this situation is that because S,,
introduces a changeofhand, even when there is no CT symmetry plane present, the
molecule contains its own mirror image.
Molecules that exhibit only C, symmetry are often termed dissymmetric: an
asymmetric molecule has no symmetry, so that chiral molecular species are those
that are either asymmetric or dissymmetric.
2.5 A BRTEF LOOK AT VECTORS AND MATRICES
In this section, we describe some of the elementary operations with vectors and
matrices that can be used to add a degree of conciseness and elegance to the
manipulation of symmetry operations. In chemistry, vectors and matrices tend not to
be among the more popular topics for study; indeed, a significant amount of
chemistry can be studied quite satisfactorily without them.
A vector differs from an ordinary number, or scalar, merely by having a direction
in space; a matrix is a collection of numbers that can be manipulated en bloc. With
a little practice, we shall gain a familiarity that will render the study of symmetry
and group theory remarkably straightforward.
2.5.1 Sum, difference and scalar (dot) product of two vectors
Let rl and r2 , Figure 2.10, be any two vectors from an origin 0. Their difference r2
 rl is the vector roc, which may be represented also by the vector from A to B, rm.
The magnitude roc (=rm) is obtained by forming the dot product of roc (from 0 to
C) with itself, and expanding the resulting expression algebraically, noting that a
dot product rl rJ is dejned by
(2.9)
rr rJ =rl rJ cos(rlArJ),
where rlA rj is the angle between rl and r, ; here, rlAr, =0 so that
2 2
rZoc =roc roc =(r2  r,)(r2  rl) =r , +r  2rl r2 cOs(8). (2.10)
It may be noted that r2 cos(8) is the projection of r2 on to the direction of rl so that
the product of rl and r2 cos(0) acts along the direction of r l . We may recognize
(2.10) as an expression of the extension of Pythagoras's theorem t o the obtuse
angled triangle OAB.
Any vector r from the origin of orthogonal axes to a point x, y, z may be written as
r =xi +yj +z k, (2.11)
Sec 2.51 A Brief Look at Vectors and Matrices 21
where i, j and k are vectors of unit magnitude (unit vectors) along the x, y and z
axes, and x, y and z are the coordinates of the termination of the vector r, or the
C R
Fig 2.10 Vectors rl and rz &om a common origin 0.
lengths of the projections of the vector on to the axes, in the same order. From (2.9),
we have
(2.12) 3 =x2 +y2 +z2.
Unit vectors on orthogonal axes obey the rule, from (2.9):
i.j =6,, (2.13)
where 6, is the Kronecker delta. This notation is simply shorthand for saying that i.j
=1 when i =j but is zero otherwise, and applies to all pairs of i, j and k.
The dot product relationship can be used for very straightforward calculation of
bond lengths and bond angles in a crystal structure, as we show in Example 2.2
below.
2.5.2 Vector (cross) product of two vectors
The vector product (cross product) of two vectors rl and r2 is dejined by
rl x r2 = rl r2k sin(rlAr2 ), (2.14)
where k is a unit vector perpendicular to the plane of rl and r2 , and directed such
that rl , rz and k form a righthanded set of directions (like x, y and z in Figure 2.8).
We should note here that whereas rl rz =rz rl and is a scalar, rl x r2 =rz x rl
and remains a vector. An important application of (2.14) arises in calculating the
volume of a parallelepipedon.
EXAMPLE 2.2. The x , y and z coordinates of the hydrogen atoms in the water molecule are
given, in order, as 0.024, 0.093, 0.000 nm and 0.096, 0.000, 0.000 nm, with respect to
oxygen at the origin of orthogonal axes. We calculate the bond angle H6H. The 0H bond
lengths are clearly 0.096 nm. From (2.9),
(0.024i +0.093j +Ok).(0.096i +Oj +Ok) =0.096' COS(HOH)
COS(HOH) = (0.024 x 0.096)/0.096'
whence H6H =104.5'. We note here that the same general equations can be employed
where the reference axes are not orthogonal.
EXAMPLE 2.3. A general parallelepipedon is characterized by the parameters a, b, c, a, j3
and y, where the edges a, b and c are parallel to the x, y and z axes, respectively. We need a
general expression for its volume V. Now, V =area of base x perpendicular height: b x c is a
22 Symmetry operations and symmetry elements [Ch. 2
V 2 =
vector of magnitude bc sin(a), the area of the base, along the direction of k, perpendicular to
the bc plane, and the perpendicular height is ak. Hence, V =a( b x c), or one of its cyclic
permutations, that is, b.(c x a) or c.(a x b).
a a + a a + a a a b + a b + a b a c + a c + a c
1 1 2 2 3 3 1 1 2 2 3 3 1 1 2 2 3 3
1 1 2 2 3 3 2 2 3 3
1 1 2 2 3 3 1 1 2 2 3 3 1 1 2 2 3 3
b a +b a +b a blbl+b b +b b blcl+b2c2+b3c3 I
c a +c a +c a c b +c b +c b c c +c c +c c
Let a =ali +a2 j +a3 k, where al, a2 and a3 are the direction cosines of a with respect to the
x, y and z axes, respectively (see Appendix 2). Similar equations may be written for b and c.
Using (2.9) and (2.14), and substituting and expanding
V =a(b x c) =(ali +azj +a3k).(bmk  bl cj +bzclk
 bzc3i +b3cj  bmi ).
The righthand side is the expansion of the determinant (see Section 2.5.3)
2
v =
a a
1 2
v =
a*a a*b a*c
boa b*b b.c .
c*a cob C e C
I 2 c3 I
since rows and columns of a determinant can be interchanged without affecting its numerical
value, we can write
a a a
1 2 3
2
bl b2 b3
v =
c c c
1 2 3
a bl c
a b3 c
1 1
a 2 b2 c2
3 3
Multiplying the two determinants (see Section 2.5.3) leads to
Sec. 2.51 A Brief Look at Vectors and Matrices 23
which simplifies to
V =abc[l  cos’ (a)  cos’ (p)  cos’ (y) +2cos(a)cos(~)cos(y)]”’
2.5.3 Manipulating determinants and matrices
We consider next those operations with determinants and matrices that will be of
importance in our discussion and use of group theory in the ensuing chapters. For
those readers who may wish for more detail on this subject, suitable material is
indicated in the section on References and Selected Reading.
Matrices and determinants
A matrix is a rectangular array of terms av (also known as ‘elements’) that may be
combined with other matrices according to certain rules. We may illustrate a general
matrix A by the equation
A =
a a ...... a
a
a a a ...... a
a a a ...... a
11 12 13 in
21 22 23 2n
31 32 33 3n
a a a ...... a
mi m2 m3 m
(2.15)
The vertical sets of terms are called coluuins (i increasing downwards), and the
horizontal sets are rows (j increasing left to right), so that the general term av lies i
terms down andj terms across in the matrix; the size of the matrix is m x n. The
terms aii form the diagonal of the matrix, and the sum of these terms is known as
the trace x, or character, of the matrix. A onecolumn matrix is a vector, so that
(2.11) may be written as
(2.16)
We shall be concerned almost always with square matrices, that is, those for which
m =n.
It is important to distinguish between a matrix and a determinant, the latter being
an array of terms of a square matrix that represents a sum of certain products of the
terms. Lfa 2 x 2 matrixA is represented by
(2.17)
then the corresponding determinant is given as det(A) by
24
A21 = (1)2+1...i
Symmetry operations and symmetry elements
a a a
; 1 1 12 13
............. a ............ a ........
:21 22 23
a a
a a
11 12
21 22
det ( A) =
al l a12 O13
det (A) =aZ1 an aU
0 3 1 a32 a33
and its numerical value is defined as
all a22  a21 a12.
=UIIAII +a21A21 +a31A31.
,
[Ch. 2
(2.18)
(2.19)
Cofactors
In general, the value of a determinant is obtained by forming the sum of the product
of each term in a given column (or row) with its cofactor. The cofactor A, of a term
a, is the determinant of one order lower, obtained by striking out the row and
column that intersect in a, , the minor M, of a,, multiplied by (1)”l; Thus, for a
third order determinant A, Azl would be given by
a a
I a31 32 33
which, from (2.18)( 2.19), becomes
A21 =(a12 a33 a32 a13 1;
= 
a a
a a
12 13
32 33
’ ( 2. 20)
(2.21)
the unsigned 2 x 2 determinant in (2.20) would be symbolized MZl. For a 3 x 3
matrix A, given by
a a a
( 2. 22)
12 13
31 32 33
(2.23)
(2.24)
The matrix A with each term replaced by the corresponding cofactor may be denoted
by A, the cofactor matrix of A.
A determinant of any order can be decomposed systematically in this manner, and
it is clear from the foregoing that a determinant can be evaluated only for a matrix
that is square. The value of a determinant is not altered if the rows and columns are
interchanged. Thus, if A is modified to A” by interchanging the rows and columns,
then
Sec. 2.51
1 0  1 2
0 1 0 2
1 1  1 0
2 1 0 3
A =
A Brief Look at Vectors and Matrices
*
25
(2.25)
i e t ( A ) = (1)
and it is easy to show that
det(A) =det( A) . (2.26)
The matrix A is known as the transpose of matrix A: the terms have been
interchanged, or transposed, across the diagonal, or the line of a,, terms. If for any
matrix a, =a,, for all i andj, the matrix is termed symmetric. A symmetric matrix
and its transpose are equal, that is, a, =a”,, for all i andj, whereupon we would then
writeA =A.
0 1 0
1 0 2 0 1 2
1 1 o + (1) 1 1 0  (2) 1 1 1
1 0 3 2 1 3
2 1 0
EXAMPLE 2.4.
determinant
We illustrate ( 2. 20H2. 24) by finding the value of the fourthorder

: 1 }= 3 + 2 + 3  2 + 4 + 4 = 8.
Addition and subtraction of matrices
The sum or difference of two matrices is obtained by takmg the sum or difference of
similar terms; thus, the general term c, of the sum or difference of two matrices A
and B is given by
(2.27)
Qy f b, =C,J’
and the result for the two matrices in their entirety is written as
A f B = C . (2.28)
It should be evident that matrix addition is commutative, that is,
A +B = B + A , (2.29)
26 Symmetry operations and symmetry elements
but with subtraction, generally
A  B f B  A .
[Ch. 2
(2.30)
Multiplications of matrices
The multiplication of two matrices will be expressed symbolically as
AB =C. (2.3 1)
For the product AB to exist, the number of columns of A must be equal to the
number of rows of B. Matrix C will then have the same number of rows as A and the
same number of columns as B: thus, if A and B have the dimensions m x n and n x
p respectively, C will have the dimensions m x p, with its terms given for all i andj
bY
n
( 2. 32)
The term cV lies at the position in C that corresponds to the intersection of the ith
row andjth column of matrices A and B, respectively. The process of (2.32) might
be summarized as ‘along the row and down the column’: for example, if A and B
are both 3 x 3, matrices, ~ 2 3 is given by
3
+ a b

23 = 1 a2k bk3  a21b13 + a22b23
23 33’
k= 1
and the position of c23 in C is shown below:
all a12 a13 ) bll ’12 b l 3
a. ...............a ....... ........a ........ j b q q ........................................
21 22 23 1 I b21 22 i 23
31 32
a a
( 2. 33)
c
: 23
A B C
More than two matrices may be multiplied together: for matrices A, B and C, a
product may be written as
A B C = D , (2.34)
where D is reached in stages, A(BC) or (AB)C, since the associative law (2.7)
applies to matrices:
ABC =A(BC) =(AB)C . (2.35)
The dimensions of D are (number of rows of A) x (number of columns of C). The
distributive law (2.6) also holds for multiplication, that is,
A(B +C) =AB +AC. (2.36)
Sec 2.51 A Brief Look at Vectors and Matrices 27
Weshould note carefully, however, that matrix multiplication does not necessarily
commute, that is, in general
AB f BA. (2.37)
If a matrix is multiplied by a scalar constant k, each term of the matrix is multiplied
by k.
EXAMPLE 2.5. We consider addition, subtraction and multiplication of the 3 x 3 matrices A
and B:
( p [: 1: B ]
A B
Following (2.27) and (2.32):
[ b ; ;]
A + B
What are the results of B  A and BA?
Inversion of matrices
Division with an operator is accomplished by forming the inverse of the operator. A
matrix which has a nonzero determinant is said to be nonsingulur, and has an
inverse A' such that
(2.38)
where E is the identity matrix. Any indicated division, such as AIB must be
rewritten as A B" . Since a determinant is defined only for a square matrix, it follows
that the inverse of a matrix exists only if that matrix is square.
The inversion of a matrix is considered in detail in texts on matrix algebra,
frequently in conjunction with the solution of sets of linear simultaneous equations.
The result that weneed here, using matrix A in (2.22) as an example is:
AIA =A1 
 E,
A21 A31
A1 = &(A) [ A12 %? A32 '
A13 A23 A33
(2.39)
where A, are cofactors, given as in (2.20). Comparison with (2.22) (or 2.25) shows
that this matrix is the transpose of the cofactor matrix of A divided by det(A). It is
clear from this equation that a nonzero value of det(A) is a prerequisite for matrix
inversion.
The inverse (AB)' of the product of two matrices A and B is formed from
( ~~1 1 =B I A ~ : (2.40)
28 Symmetry Operations and Symmetry Elements [Ch. 2
for leftmultiplication by (AB) leads to
(AB)(AB)' =(AB)(B'A') =A(BB')A =AE4l =AA' =E,
(2.41)
so that B'A' is the correct inverse of the product AB.
The inversion of a matrix through (2.39) is feasible with matrices up to 3 x 3 in
size, but for higher orders it is labour intensive and one alternative method will be
discussed in the next section.
EXAMPLE 2.6. We now find the inverse of the matrix A in Example 2.5.
Following Example 2.4, det(A) =1. From (2.20), the cofactor matrix becomes
We now transpose A and divide by det(A):
2 2  1
A' =  x = [I  1 I ]
det'A) 1  2 1
It is left to the reader to confirm that AA' =A'A =E.
Orthogonality
A matrix A that fulfils the condition
A" =A"
(2.42)
is said to be an orthogonal matrix. All orthogonal matrices are square (n x n) but
not necessarily symmetrical, as in the following example
(2.43)
Here we find det(A) =1, and
2.5.4 Eigenvalues and eigenvectors
Many procedures in theoretical chemistry involve eigenvectors and eigenvalues, so
we shall establish a brief background in these topics.
An eigenvalue equation has the general form
Of = (2.44)
where 0 is an operator and f is a function that is the same on both sides of the
equation, an eigenfunction; h is a scalar constant, an eigenvalue. The wave equation
Sec 2.51 A Brief Look at Vectors and Matrices 29
that we shall meet in later chapters is a well known example of an eigenvalue
equation.
For any square matrix A of order n, we can write an eigenvalue equation of the
form
Ax =hx (2.45)
where x is a column vector, or an n x 1 matrix (Section 2.5.3), and h is a scalar
quantity. There are n solutions of t hi s equation, leading to n eigenvalues h, and n
eigenvectors x. If an eigenvector is multiplied by a scalar it remains an eigenvector,
and the eigenvalue is unchanged: with any scalar a, using (2.2) and (2.45)
(2.46)
so that (ax) is also an eigenvector, with the eigenvalue h.
In order to find the eigenvalues and eigenvectors of an n x n matrix A, we begin by
writing (2.45) as
Ax =E x , (2.47)
A( ax) =d x =ahx =h(ax),
where E is an identity matrix
1 0 0 0 0
' = [ : l o ""j (2.48)
0 0 0 0 1
We choose the order of E to be n, to match that ofA; then we can write
(AWX =0 (2.49)
If the vector x is nonzero, the matrix (A  hE) is said to be singular provided that
det(A  hE) =0 (2.50)
and the equation may then be solved for the eigenvalues and eigenvectors.
Conversely, given (2.50), there exists a nonzero vector x that conforms to (2.49)
which, in turn, means that (2.47) holds, and h is an eigenvalue of A. In other words,
and generally, h is an eigenvalue of a matrix A if and only if det(A  hE) =0.
Equation (2.50) is termed the characteristic equation of A in the variable h, and its
roots are the eigenvalues of A.
EXAMPLE 2.7. We find the eigenvalues and eigenvectors of a 2 x 2 matrix A.
Thecharacteristic equation becomes:
30
D = Q ~AQ =
Symmetry Operations and Symmetry Elements
[Ch. 2
o q o ............ 0 0
O O r .............. 0 0
0 0
. I
. I
. .
. . , .
. I
. I
. I
, . , *
or
whence the eigenvalues h are 3 and 1. We now find the eigenvectors of A. For h =3:
h2  2h  3 =o,
A  hE=(;;) 3(;;) = (2 2  2 2 ) ’
From (2. 47):
Thus, we obtain:
 2 x + 2 y = o
2x  2y =0 (redundant)
We add to these equations the vector noxmalizing condition
2
x +y2 =1,
whence the eigenvector becomes [: 2 . Similarly, for h =1, we find the eigenvector is
Diagonalization
A diagonal matrix is one in which all offdiagonal terms are zero; the identity
matrix E is a special form of a diagonal matrix in which also all diagonal terms are
unity, (2.48). Thus, an identity matrix E is characterized by the conhtion
e . =6. . (2.51)
In general, a nonsingular matrix A (see Section 2.5.3) that has eigenvalues taken
in the order p, q, r, ... can be diagonalized by another matrix Q, the columns of
which are the eigenvectors of A taken in the same order. Then, the diagonalized
v v
( 2 . 5 2 )
Sec. 2.51 A Brief Look at Vectors and Matrices 31
Similarity transformation
The product Q"AQ is known as a similarity transformation of A by Q: the action of
Q is mitigated by that of Q', leaving D with a nature similar to that of A, with equal
determinants, eigenvalues and traces:
det(A) =det(D), (2.53)
W) =W), (2.54)
X ( 4 ' X O . (2.55)
Similarity transformations are encountered in several areas of theoretical chemistry.
Two matrices A and D with equal traces, or that can be diagonalized by another
matrix Q, are said to be conjugate matrices (see Problem 2.13).
EXAMPLE 2.8. Following on Example 2.7, and fromthe above discussion, we can
diagonalize A by a matrix Q that has columns which are the eigenvectors of A taken in order.
Since Q =Q' here,
We note that the two eigenvectors from Example 2.7 are orthogonal: their dot
product (see Section 2.5.1) is given by
(id2 +j42) * (i 42  j42) =0.
Jacobi diagonalization
The above technique of diagonalization is straightforward with matrices of order up
to 3, but it becomes very cumbersome with larger matrices and a more convenient
method is needed: one such procedure is the Jacobi diagonalization. We discuss this
approach in Appendix 4, where we show that a 2 x 2 symmetric matrix A can be
diagonalized by a rotation matrix Q, with A exemplified by
A = (; ; ) ;
(2.56)
Q is now the twodimensional part of (A4.3), or (2.43), indicated here by the dotted
enclosure:
(2.57)
.... sin ( e ) ~
0
In general, for any symmetric 2 x 2 matrix A
(2.58)
the value of 8 that forms the diagonalizing matrix Q is shown (Appendix 4) to be
given generally by
32 Symmetry operations and symmetry elements [Ch. 2
tan(20) =2a12/(all  u ~ ~ ) ;
(2.59)
with 0 =45" , the result obtained in Example 2.8 follows. Now consider any n x n
symmetric matrix A, and let the terms a,, , Q,, , u,, and uu which, themselves, form a
2 x 2 symmetric matrix, be isolated and diagonalized by the Jacobi procedure. The
appropriate 0 rotation is obtained following (2.59), with the transformation Q'AQ
operating only on the selected terms. Generally, the largest offdiagonal terms are
located and the procedure iterated until each offdiagonal term is less than a
prescribed, sufficiently low quantity. As diagonalization is of importance in the
applications of group theory, we study a final example here (see also Appendix 12).
Example 2.7. We find the eigenvalues of the matrix A by J acobi diagonalization.
A = & 1 8 &
[ :::",:
We isolate the 2 x 2 matrix A4 with the largest offdiagonal terms:
From (2.59)
tan(20') =2 x 7/(15  15).
Hence, 81 =d4, and the diagonalizing matrix Ql is from (2.57)
Cos (814) 0 sin(K/4) 0 1
sin(K/4) 0 cos(n/4)
Q l = [ o 1
whence, from (2.52), remembering that for an orthogonal matrix Q, Q' =& we
obtain
1 5 d b 7 0 1 22 2d3 0
Q, 1 AQ = I[! 2 {i ] [ d; ;; 21 [ i d i ;] = k 3 1; CJ].
We now operate on the result of this product in a similar manner, taking the one remaining
pair of offdiagonal term; thus,
tan(202 ) =4 x d3/(22  18),
and 82 =7d6. Hence, the second diagonalizing matrix Q2 becomes
cos(Tt /6) sin(Tt/6) 0 d 3/ 2 112 0
sin(K/b) cos (11/6) o ] = [ 1;dr2;],
Q2 = [ 0 0 1
Sec. 2.51 A Brief Look at Vectors and Matrices 33
whence
d3/2 112 0 22 2d3 0 3/2 1/2 0
112 d3/2 0 ] [ ,”” A8
0 0 1 ] [ ‘li2 dy ]
24 0
0 16
0 0 8
Hence, the required eigenvalues are 24, 16 and 8.
It may be noticed that i n the lasl example CIAri =x( A) =48, and that the same
result has been obtained for the final diagonalized matrix. That this result is general
may be shown as follows.
Let A’ be the matrix obtained by the similarity transformation
A‘ =Q”.4Q
By definition
(2.60)
X V ’ ) =ci AIii (2.61)
and, using (2.32). the righthand side of (2.61) niay be recast as
Ci A’ii =Ci c k Q &“4k@li. (2.62)
This equation niay be reordered such that
Xi kit =C k CIAkl Xi Q;l’ e l k
=C k && (Q’Q),k, (2.63)
from (2.32). Now, Q’Q =E =61, , and a nonzero result will be obtained wi thj =k,
whence
(2.64)
xV’) =Xi 24’ii =C, A, =XU)
which shows that the character of a matrix, or representation (q.v.), is invariant
under a similarity transformation of that matrix.
2.5.5 Blockdiagonill and other spccial matrices
A particular case of matrix multiplication exists with matrices having nonzero
values in blocks around their diagonals. for example:
0 0 0
5 0 0
la 0 0 0
( 2. 65)
This multiplication may be considered i n terms of itsfuctors, or submatrices:
34 Symmetry operations and symmetry elements [Ch. 2
The product in (2.65) is blocked in the same way as in the original matrices, and we
shall make use of this block form of matrices in discussing representations and their
applications. There are several other special matrices that we shall consider briefly
here; they, too, will be of use in later chapters.
Adjoint and complex conjugate matrices
The adjoint At of a matrix A is defined as the complex conjugate of its transpose:
At (2.67)
that is, atv =."f =a ; for all i and j , and the following matrices provide an
example.
conjugate matrix is given here by replacing i throughout by 1.
Real matrix
A real matrix A has the properly that av =a ; . , so that a real matrix is identical to
its conjugate:
A =A'
Hermitian matrix
A matrix A is hermitian if it is equal to its adjoint:
A = A ~
that is, aV =atv =a"; =a f for all i andj; the following matrix is Hermitian:
i  i
l i e 1 i e
i 2 4
e 4 5
i
?i
I :i : : 1
I
A
Clearly, the complex conjugate ofA, which is At here, is equal to A.
(2.68)
(2.69)
Sec. 2.51 A Brief Look at Vectors and Matrices 35
Unitary matrix
A matrix is unitary if its adjoint is equal to its inverse:
At =A '
(2.70)
that is, aty = a i' for all i andj; matrix A below is unitary (see also Appendix 6).
In Table 2.1 the types of matrices and some of their properties that we have
discussed in this chapter are summarized. It completes our introduction to the
matrix methods that will be useful in studying point groups and molecular
symmetry. The reader is encouraged to practice the matrix manipulations described
here. Further discussions on matrices and determinants may be found in the
standard literature['' ' I .
Table 2.1 Matrices and matrix properties
A
A Matrix, transpose of A : =aji.
At
Al
A
det(A) Determinant of matrix A : I
Mi,
%(A)
E
Diagonal matrix: a,, =ki 6, (ki f 0)
Hermitian matrix: aii =aty =a" ; . =a fi
Orthogonal matrix: a", =a ;' =aj,.
Matrix: for our purposes, square and often 2 x 2 or 3 x 3
Matrix, adjoint of A : ut =a" ; . =u :,i .
Matrix, inverse of A : a i' =A,, ldet(A)
Matrix, cofactor related to A: A, =(l)i+'A4w
Minor determinant of element ay of matrix A
Trace, or character of matrix A: x( A) =Ci Air.
Identity matrix: eii =S,, (Specialized diagonal matrix)
a, . =0
Null matrix: 11
Real matrix: 11 11
*
a. . =a , .
Symmetric matrix: ay =a", =qi
unitary matrix:
ati, =a;' =8.. =a*.
11 I'
PROBLEMS 2
2.1 Simple, where possible, the following expressions involving the operators
2
D = L( ),Dz=
( ),L =l n( ) , x=x (
dx dl?
Operator Function
36 Symmetry operations and symmetry elements [Ch. 2
(a) D
x3 +sin(x)
(b) L
x +exp(ax)
(c) D2
kX2+X
(dl ( X+ D)
ax'
(e) DXD x2 +1
(f) [D(X +D)1 x3
2.2 Two atoms have the coordinates given below. Calculate yAB assuming (a)
orthogonal coordinates, and (b) the angle zAx =120".
Atom x/nm y/nm z/nm
A 0.20 0.30 0.42
B 0.05 0.15 0.21
2.3 (a) Which of the species illustrated by Figures 1.1, 1.3c, 1.3d, 2.2, 2.4, 2.5, 2.6
and 2.9 are asymmetric, and which are dissymmetric'? (b) How may the symmetry of
the molecule in Problem 1. lc, projected on to the molecular plane, be described?
2.4 Refer to Problem 1.2. What symmetry elements are present in (a), (b), (c), (0,
(g) and (h)? Where two or more elements are present, give their relative orientation,
with respect to features of the object.
2.5 What symmetry element or elements arise from each of the following
conibinations. where both elements in each pair pass through one and the same
point'?
(a) C2 and 01,; (b) S4 and q (S4 in 0"); (c) C3 and i; (d) s6 and C2 (I s6).
2.6 What setting of orlhogonal axes would be appropriate for each of the following
molecules? Which spccies would exhibit optical activity'?
(a) benzene, ChH6: (b) water. H20: (c) methane, CH4; (d) 1,ldichloroethene,
C2H2C12; (e) trans 1,2dichloroethene, C2H2C12; (Q 2chloropropanol,
CH2(C1)CH20H: (g) 1 chloropropanol.
2.7 Obtain (a) A +B, (b) '4  B, (c) x( B) , (d) det(A), (e) the cofactor matrix of A, (f)
AB, and (g) '4l , given
2 3 1 2 4 6
B = 8 10 8 .
A = [ ; ; $1; i14 * I
1: 2 : : ]
2.8 Diagonalize the matrix A by the J acobi method, and list the eigenvalues and
normalized eigenvectors: '4 = 2 6 I o
2.9 From Figure 2.1. any general vector r(x, y , z) is rotated to the position r' (x', y' ,
z) by the operation C4 . Write this transformation as a matrix C that multiplies the
column vector r. and obtain thc similarity transformation on C4 through the matrix
R that represents 0, symmetry across the xz plane. What symmetry operation is
represented by this product?
Problems 31
2.10 Given matrix A, identlfy matrix B in each of the following examples [E =
exp(ia), where a is a constant]:
A = [  : 0 f I ]
(a)
2 i 2e
B = [i * o* ;; 1
2e ie
2.11 By vector methods find the angle between (a) any two facedragonals of a cube,
(b) the body hagonal of a cube and one of its fourfold rotation axes, say y, and (c)
the angle between the body diagonal of a tetragonal parallelepiped and its fourfold
symmetry axis (z); let the sides of the paralIelepiped be a, b and c, where a =b and
cla =312.
2.12 The matrix A corresponds to an anticlockwise, fourfold rotation of a vector
about the z axis in an orthogonal reference frame x, y, z. From the procedure in
Section 2.5.4 diagonalize the matrix A and find the eigenvalues and normalized
eigenvectors. From the eigenvectors construct a matrix that will hagonalize A, and
carry out the diagonalization of A by a similarity transformation. Finally, write the
complete diagonal matrix.
3
Group theory and point groups
Yet it is natural for man,
more than for any other animal,
to be a social and political animal,
to live in a group.
St Thomas Aquinas (12251274): On Kingship
3.1 INTRODUCTION: GROUPS AND GROUP THEORY
In this chapter we shall discuss the topics of group theory and point groups. We may
look upon group theory as a tool for handling symmetry operations and their
combinations in a quantitative manner, leading to an elegant procedure for
describing the role of symmetry in chemistry. A point group provides a concise
description of the symmetry of a finite body, and all finite bodies may be classified
in terms of their pointgroup symmetry. The set of symmetry operations comprising
a point group constitutes a mathematical group.
3.2 WHAT IS GROUP THEORY
Group theory deals with sets of operations having the property that, when two
operations of the set are carried out successively, the result is that which would be
obtained by another single operation of the set, starting from one and the same
initial situation. A set of operations forms a group provided that it satisfies this
condition together with a number of group postulates.
3.2.1 Group postulates
A group consists of a set of mathematical objects that may be symbolizedby E, A, B,
C, ..., called members (also known as 'elements') of the group. In our discussion of
group theory the members of the group will be, normally, symmetry operations, and
they will be written in bold type. Thus, a symmetry group may be written
collectively as 6{E, A, B, C, ...}, and all groups are governed by the following
group postulates.
Closure
The combination of any two members of a set is also a member of the set; this group
property is referred to as closure, and is implicit in Figure 1.4. The combination of
the members is termed their product irrespective of the nature of the combination
process; it will generally, but not necessarily, be multiplication. We may write a
product as
BA=C, (3.1)
Sec. 3.2] What is Group Theory 39
where C is a member of the set A, B, ..., and we need to indicate the law of
combination. If the law of combination is multiplication, then the group is said to be
closed with respect to multiplication.
Laws of combination
In the case that the law of combination is multiplication, we have shown in Section
2.5.3 that the order of multiplication, normally, is important: if (3.1) represents a
combination by multiplication then, in general, the reverse order of multiplication
leads to a different result:
AB=D, (3.2)
but where D is also a member of the set A, B, C, .... Other laws of combination are
inter alia addition, matrix multiplication and vector addition.
Association
The associative law (see also Section 2.2) holds for multiplication, that is,
A(BC) = (AB)C.
IfBC = Z, and with (3.2), it follows that
AZ= DC.
(3.3)
(3.4)
Identity member
The group contains the identity, or unit, member E (see also Section 2.2.7), such
that
AE = EA = A
for each member of the set.
(3.5)
Inverse member
Each member of the set has an inverse (see also Section 2.5.3) that is also a member
of the set; thus,
(3.6)
We see that these postulates are paralleled by the operations of matrices: this
property will be taken up in later chapters, where we can introduce notation to
distinguish between a symmetry operation and the matrix used to represent its
action.
3.2.2 General group definitions
a) A group may be finite, the number of members of the group being the order h of
the group, or infinite. Thus, 6{E, A}, A
2
} is finite, but 6{E, AI, A
2
, ... , oo} is
infinite; infinite groups have an important role in spacegroup theory.
b) An abstract group is concerned only with the relationships in the set of
operations, there being no specific interpretation attached to the members of the
group. Thus, 6{E, A}, A
2
} could be a finite, abstract group, since no meaning is
attached to the members other than E.
c) A group in which all the members commute (see Section 2.5.3) is called an
Abelian, or commutative, group. Thus, the group 6{E, AI, A
2
} , where EA
i
=
40 Group Theory and Point Groups [Ch.3
A;E (=A;) andA;Aj=A;1; (i,j = 1, 2), is an example ofa commutative group. It
is possible for a group to be nonAbelian although some of its members commute;
point group D
4
., which we shall meet later, is one example.
d) A group consisting ofa single member A and its powers zl ' , A
3
, •.. , AP, is called a
cyclic group of order p, where p is the smallest integer for which AP= E. Figure
2.1 illustrated the cyclic group C
4
of order 4, containing the symmetry operators
C
4
, C ~ (= C
2
) , C ~ (= C4
1
), C: (= E). We see that operating with C
4
twice in
succession takes us from (a) to (c) via (b), and that operating with C
2
on the
initial state takes us from (a) to (c) directly; thus, C
2
is properly a member of the
group C
4
. We note also that the symmetry element C
4
is associated with more
than one symmetry operation, as discussed already in Section 2.2.
e) A subset of members of a given group forming another group is a subgroup of
the given group; the given group may, in turn, be termed a supergroup of the
subgroup. Thus, a group consisting of the members C
2
(= C 2
1
) and C ~ (E), is a
cyclic group of order 2, C
2
, and a subgroup of the group C
4
which, itself, is a
supergroup of C
2
.
f) Every geometrical body, crystal or molecule in our applications, may be
characterized by a group known as a point group, which is of finite order, except
for those containing the operation CX> , such as exists for the HF or CO
2
molecules, for example.
g) The properties of the members of a group may be presented conveniently as a
group multiplication table (Section 3.2.3), again irrespective of the law of
combination. The members of the group are listed in the top row, identity first,
and again in the lefthand column. An entry in the top row represents the
operation first applied, and that in the lefthand column the second operation;
the combination member falls in the appropriate position in the body of the
table. The order of operations is important, as indicated in Section 3.2.1, and it
is that used normally in mathematical equations. For example, in evaluating
exp[sin(x)] we find first sin(x) and then carry out the exponentiation of the
resulting value.
h) Two groups 6 and 6' are described as isomorphic if there is a onetoone
correspondence between the members of the groups, that is, the combination C =
AB in group 6{E, A, B, C} implies the combination C' = A'B' in the isomorphic
group 6 / { E ~ A ~ B ~ C'}.
i) Two groups 6 and 6' are termed homomorphic if they are similar in structure
and have the same group multiplication table. If we associate the groups 6{E, A,
B, C} and 6' {l, I, I, I} in the following manner,
E ABC
1 I I 1
they show a twotoone correspondence, because two members of 6 are
associated with one member of6': they have the same group multiplication table
(see Section 3.2.3), and are homomorphic.
Sec. 3.2] What is Group Theory 41
3.2.3 Group multiplication tables
We examine here three groups that will illustrate and elaborate some of the
principles just discussed.
a) Consider first an abstract group of order 3 consisting of the members E, A, and
B, and for which the relations A
2
= Band AB = E hold under multiplication; the
group table may be written as
E
A
B
E
E
A
B
A
A
B
E
B
B
E
A
b) A cyclic group of order 3 comprises the members Z, Z2 (= Z1) and Z3 (= E)
under multiplication; the group table becomes
E
z
E
E
z
z
z
E
E
z
c) Finally, consider the group of order 3 comprising positive integers modulo 3,
with addition as the law of combination; the group table is as follows:
a
1
2
a
a
1
2
1
1
2
a
2
2
a
1
These three groups are isomorphic. There is a onetoone correspondence between
the members of the groups:
A ~ Z ~ I
B ~ Z 2 ~ 2
C ~ Z 3 ~ O
The groups are also Abelian; this nature is revealed through the symmetry across
the principal diagonals of the bodies of the group multiplication tables. We note also
that no member of a group is repeated among any row or column within a group
table.
42 Group Theory and Point Groups [eh.3
An important group in studying crystal symmetry is the translation group: the
basic translations a, band c that define a unit cell in a threedimensional lattice
comprise an infinite group of the form
(3.7)
The law of combination is vector addition, and the zero vector (nl = n: = n3 = 0)
represents the identity operation; the negative signs on n, introduce the inverse
members of the group.
The power of the group multiplication table enables us to write out the tables
without necessarily knowing first all the relations between the members. For
example, in Problem 1.2(d) we found a C
2
axis and two perpendicular mirror planes
intersecting in that axis. We denote these planes by cry and o ~ , and we can
immediately set down a partial group table of the corresponding symmetry
operations:
E C
2
cr,
a,
E E C
2
cr, cr,
C
2
C
2
o; cr,
a, cr
v
It is not difficult to enhance it immediately, because of the nature of C
2
and o
themselves; each operation is its own inverse:
E C
2
cry cr
v
'
We now have to decide whether C
2
cr, = c, or C
2
cr, = a
v
' . If we choose the former
then column 3 within the table would contain o, twice, which is not permitted;
hence, we must write C
2
cr
v
= o, , whereupon the remainder of the table can be
completed:
C
2v
E C
2
a
v
a
v
E E C
2
cr,
a
v
C
2
C
2
E a
v
cry
o, a
v
cr
v E C
2
cr
v
a
v
o; C
2
E
We shall refer to this table again; it relates to the point group C
2v
(C, 'cyclic'), which
is Abelian, order 4. It is of frequent occurrence: for example, water, tetrafluoro
sulfur, chlorobenzene and the cisdibromodichloroplatinum (II) anion all share this
group.
Sec. 3.2] What is grout) theory 43
3.2.4 Subgroups and eosets
We introduced subgroups briefly under Section 3.2.2, and here we discuss them
more fully. The group multiplication table for above indicates three subgroups:
the identity group £.{E}, or C
1
{E}, the group C
2
{E, C
2
} and the group C. {E, o},
If we remove all reference to the operation C
2
in that is, C
2
and one c, because
C
2
= o,o , we are left with the operations E and cr. They form the subgroup C. :
C.
E
rr
E
E
o
c
E
There is only one way in which C. may be derived from C
2v
, for which reason it is
called an invariant subgroup of its supergroup C
2v
. The other subgroups of C
2v
are
also invariant, as shown by Figure 3.1. It does not follow that these subgroups are
necessarily invariant with respect to other supergroups, Figure 3.1 (see also Problem
3.4). The order g of a subgroup is always an integral submultiple of the order h of
the corresponding supergroup, that is, g = hln, where n is an integer greater than
unity.
The point group D
2h
may be written D
2
h{E, C
2
(z), C
2
(v), C
2
(x), i, cr(xy), cr(zx),
cr(vz)}. One subgroup of D
2h
is D
2
{E, C
2
(z), C
2
(v), C
2
(x) } . We can form the product
of each member of D
2
with a member of D
2h
that is not also a member of D
2
, say,
cr(xy). If we carry out the rightmultiplication of D
2
by the set D
2
cr(xy ) obtained is
termed the a right coset of D
2
:
D
2
cr(xy ) = Ecr(xy), C
2
(z)cr(xy ) , C
2
(v)cr(xy), C
2
(x)cr(xy )
= cr(xy), i, cr(vz), cr(zx).
Thus, the group D
2h
can be represented by the combination of D
2
and the right coset
of its subgroup D
2
with under addition:
D
2h
= D
2
+
Left cosets may be constructed in an analogous manner.
44 Group Theory and Point Groups
v AI'
~ .. "0 "
[Ch.3
(3.10)
~
1
Fig. 3.1 The thirtytwo crystallographic point groups and their subgroups; thin lines indicate
the subgroups that are invariant. Thus, C2v is an invariant subgroup of D2d, C4v and D2h, but
not of C6v or D3h
3.2.5 Symmetry classes and conjugates
Subgroups provide one method for separating the members of a group into smaller
sets, each constituting a group. An alternative procedure introduces the topic of
symmetry classes. In Section 2.5.4, we introduced the similarity transformation; we
now use this concept to discuss symmetry classes. If two symmetry operations A and
B of a group are linked to a third operation R by the equation
B = R1AR, (3.8)
then B is the similarity transformation of A by R, and A and B are said to be
conjugate to each other. Conjugate members of a group have useful properties, as
follow:
a) Every member of a group is selfconjugate, that is, for any member A
A = R1AR: (3.9)
for leftmultiplication with A'I leads to
A,IA = E = A,IR1AR = (RAYI (AR),
following Section 2.5.3. It follows that RA = AR so that R and A commute; R may
be just E, which is always present, or any other member that commutes with A.
Sec. 3.2] What is grout) theory 45
b) If A is conjugate to Band B is conjugate to C, then A is conjugate to C. We
have
A = R'BR,
B = Q'CQ.
Substituting for B in (3. 11) leads to
A = RIQ1CQR = (QRrlC(QR) = ZICZ,
(3.11)
(3.12)
(3.13)
where Z (= QR) is also a member of the group, conjugate to A.
c) As a corollary to (b), by putting C = A in (3.11H3.12), it follows that if A is
conjugate to B, then B is conjugate to A.
We define a symmetry class to comprise those members of a group that are
conjugate one to the other. This definition may be illustrated with the aid of the
group tables that we have already discussed. We take the cyclic group of order 3,
C
3
{E, Z, Z2}, and perform a similarity transformation of each member by each
member of the group, with the following results:
E: K1EE = EE = E Z'EZ = ZI
Z
= E (Z2
r'EZ
2
= (Z2
r
1Z2
= E
Z: K1ZE = ZE = Z Z'ZZ = EZ = Z (Z2
r
IZZ2
= (Z
2rIE
= Z
Z2: K
1
(Z2)E = Z2 ZI (Z2)Z = ZI E = Z2 (Z
2r'
(Z2)Z2 = EZ
2
= Z2
It is evident that this cyclic group contains three symmetry classes, each with one
member, E, Z or Z2. It is left as an exercise to the reader to show that the group
{E, C
2,
o, , 0" } contains correctly the four symmetry classes E, C
2
O"y and 0" .
We shall content ourselves with one more example group, that exhibited by the
trigonalpyramidal ammonia molecule and symbolized by C3y; its order is 6 and the
group multiplication table is given below. We work through one member, C
3
, and
leave the remainder as an exercise for the reader (see also Problem 3.5).
C3y E C
3
O"y O"y o"v
E E C
3
"
O"V O"y O"y
C
3
C
3
E
"
O"y O"y O"v
C
2
E C
3
"
:J
O"y O"V O"y
"
E
C
3 O"V
0",. O"y O"y
"
C
3
E
O"y O"y 0",. O"y
" "
C
3
E O"y O"y O"y O"y
K
IC
3E
= C
3 O"vl C
30"v
O"v_IO" y = O"vO" v
(C
3r
l
C
3C3
= EC
3
C
3
'I ' "
= = 0" v  C
30"
v O"yO"y
(C r'c, C = rlE C
3
0" O"V = C
46 GrOUI) Theory and Point GroUI)S [eh.3
From the results just obtained, it follows that the operations C
3
and C:1 belong to
one and the same class in this group. In a similar manner, cry, o v and o ~ form a
single class, and we write the classes for C3y as
E
The orders of classes must be integral submultiples of the order h of the group. In
group C
3
, the classes are E, C
3
and C 3 : the operations C
3
and C:1 do not combine
into one class in this group; there is no other operator in the group that will combine
with C
3
to give C ~ . In fact, all symmetry classes of Abelian groups comprise single
symmetry operators.
We need not necessarily engage in the labour of performing these similarity
transformations each time we need to determine the symmetry classes of a given
group. It will be sufficient to separate those operations that are themselves
equivalent under a symmetry operation of the group. Thus, in the group that we
have just considered, the three cry operations are equivalent under C
3
, whereas C
3
and C 3 are equivalent under the cry operations: E itself always forms a separate
class in all groups; 0
1
EO = E for any chosen operator O.
3.3 DEFINING, DERIVING AND RECOGNIZING POINT GROUPS
We have remarked already that Figure 1.4 is an example illustration of group
closure, Section 3.2. I: two symmetry operations in a set were combined to produce
another operation, also in the set.
A collection of symmetry operations for a body is referred to as a point group,
which may be defined formally as a set ofsymmetry operations, the action ofwhich
leaves at least one point of the body invariant, or unmoved. A similar definition
may be expressed in terms of symmetry elements.
All symmetry elements of a point group pass through the invariant point. In some
cases it is a line or even a plane that remains invariant under the symmetry
operations of a point group. The origin of the reference axes must be a point of
invariance under all symmetry operations: otherwise, there would arise a
multiplicity of origins (and symmetry elements), which is a feature of repeating
patterns. Figure 3.2 illustrates the effect of two nonintersecting (parallel) twofold
axes; it is clear that they lead to infinite repetition, to patterns that are governed by
spacegroup theory.
3.3.1 Deriving point gmulls
The operation of rotation C, (Section 2.2.3) is defined formally for values of n from
I to infinity. However, to keep the discussion to a comfortable length, we shall
restrict ourselves at first to the thirtytwo crystallographic point groups, which
means that n can take the values L 2, 3, 4, and 6. Subsequently, we shall consider
some extensions ofn, one of which is explicit in Figure 2.2.
Sec. 3.3] Defining, deriving and recognizing point groups
.... 00
47
+
00
1 2
a b
+
00
3 4
c d
+
00
5 6
e
Fig. 3.2 Effect of two parallel twofold axes (diads) a and b, considered to be lying in the
plane of the diagram. Point 2 is related to point I by rotation about axis a; the ± signs
indicate a given, fixed distance above or below the plane of the diagram. Points I and 2
rotated about axis b produce points 3 and 4; but 3 and 4 are, themselves, related by another
diad, c. The effect of diad c on points I and 2 is to produce points 5 and 6; but they are
related to 3 and 4 by diad d, and to each other by diad e. Now 3 and 4 can be rotated about e,
and so on. This progression would lead to an infinite number of parallel, equidistant diads,
together with the symmetryrelated points, an arrangement that is wholly inadmissible under
pointgroup synunetry.
The simplest point group consists of the single symmetry element C\, which
corresponds to the identity operation E, or C\: we give this group the symbol C\, and
its order h is I. Evidently, we can write another four such simple groups C
n
with n =
2,3,4 and 6; we will refer to these groups as type (a). Another five groups are S, (n
= 1, 2, 3,4 and 6). We note here that it is conventional to refer to 5\ as C. (it has a
single symmetry plane), to 5:l as C, (it has a point of inversion, or centrosymmetry),
and to 56 as C
3h
(it has a C
3
axis normal to a symmetry plane); we call these groups
type (b).
In order to proceed further. it is necessary to consider combinations of symmetry
operations: it is evident that combinations such as EC
n
and ES
n
cannot lead to any
new groups, because E is a member of all groups, so we consider next the
combinations iC
n
..
For n = 1. iC\ = i, which was derived under type (b), as point group C
i
(5:l). For n
= 2, we have i combined with C
2
. We define a group 6{E, C
2
, i, ...}, and we can
construct a partial group table:
E C
2
E E C
2
i
C
2
C
2
E
E
It is not difficult to see that the combined effect of rotation by 180
0
and inversion
through the centre of symmetry. a point on the C
2
axis, is equivalent to reflection,
from the initial position, through a symmetry plane normal to the C
2
axis. Because
of its orientation this plane is designated Gh. The pointgroup symbol is C
2h
, and we
can now complete its group table:
48 Group Theory and Point Groups
C
2h
E C
2 ah
E E C
2 ah
C
2
C
2
E all
i
all E C
2
ah ah i C
2
E
[Ch.3
We can show the effect of the combination iC
2
graphically by means of a stereogram
(see Appendix 3). In Figure 3.3, the points have been enumerated, and we can trace
the following operations:
~ 3
i
2 ~ 4
We see that the operation C
2
followed by i is equivalent to the reflection operation
ah; we write this result as
(3.14)
In this example, the combination C
2
i gives an equivalent result; i and C
2
commute.
We recognize this equation as another example of closure (Section 3.2.1). This
group may be written as C
2h
{E, C
2
, i, all}; h = 4, and its subgroups are C\, C
2
, C,
and C, . We stress that we symbolize the reflection plane in this example as ah even
though it is set vertically with respect to the stereogram: the symmetry plane normal
to the principal C, axis is always designated ah, whatever the orientation of the
stereogram or other illustration of the group. Conventionally, the z axis (C
2
) would
be set normal to the plane of the stereogram: the variation adopted here allows the
four symmetryrelated points to be appreciated more readily on the diagram.
Proceeding in this manner for other values of Cn, we find that i combined with C,
generates all if n is even. When n is 3, i combined with C
3
generates 8
6
; the result
Fig. 3.3 Stereogram lor point group C2h; the C
2
axis (z) lies lett to right on the diagram, and
the O'h plane (x,y), indicated by the heavy line, is normal to C2.
Sec. 3.3] Defining, deriving and recognizing point groups 49
for n = I has been discussed already. Thus, the combinations of C, and i have led to
three new point groups, C:l1" C
4h
and C
6h
, denoted as type (c).
Next we may consider the combinations is,,. lt is not difficult to show that no
point groups are obtained that are not already included under types (b) and (c), and
we summarize the thirteen point groups derived so far in Table 3.1. Note the
conventional symbols for certain S, groups in type (b); the symbols in parentheses
indicate second occurrences of a group within the table.
Table 3.1 Partial set from the 32 crystallographic point groups
Type Operator/s Number of groups Pointgroup symbols
n
2 3 4 6
a) C
n
5 C
1
C
2
C
3
C
4
C
6
b) Sn 5 C, C, C
3h 54 56
c) ic, 3 (C
i
) C
2h
(56) C
4h
C
6h
Euler's construction
In order to derive further point groups, we must combine C, operations with
operations other than E or i. Until now, there has been no problem about the
relative orientations of the symmetry elements that we have used; i has been a point
on an axis. However, if we wish to combine, say, C, and C
2
, we need to know their
relative orientations. It seems likely that a C
2
axis would lie perpendicular to Cn, or
even collinear with it: but are these orientations correct, and are there other
possibilites that we should consider?
We shall discover that constraints exist that limit the number of possible
combinations of symmetry elements. whether or no we are restricting the discussion
to just the crystallographic point groups. It is instructive to carry out the necessary
analysis by a construction due to Euler. In principle, it is another application of the
group law of closure. of which (3. 14) is one example, as we have seen.
We may consider Euler's proposition first in terms of proper rotations Cn, and
then extend it to include the improper rotations Sn. A geometric illustration of
Euler's analysis is illuminating.
Let OA and OB (Figure 3.4) represent two symmetry axes intersecting at 0, the
centre of a spherical projection of a symmetrical crystal (see Appendix 3); A, Band
A' define the equatorial plane, normal to the direction through C, 0 and C'. Let
BAC = BAC' = ai2, and ABC =A iJ c = ~ i / 2 , where a. and ~ are angular rotations
associated with the axes OA and OB respectively.
Consider the motion of the line Ot'. The anticlockwise rotation «, about OA, maps
C on to C; the anticlockwise rotation ~ 1 , about OB, returns C to its original position.
The sense of rotation given here is for observation along the axis towards the origin
O. The arcs CBC and CAe' are zone circles (q.v.)for the axes OA and OB
respectively. We can think of C' as the image of C in the plane OAB. lt may help to
consider Figure A3.2 (Appendix 3), where OP would map on to OP' by an
anticlockwise rotation of 180
0
about the axis bOb'; a 90
0
rotation would have taken
50 Group Theory and Point Groups [Ch.3
P just to the point e in the equatorial plane. Similarly, an anticlockwise rotation of
180° about eOe' returns P to its first location.
A'
Fig 3.4 Partial spherical projection of symmetry directions in a body; OA and OB are the
given rotation axes.
The combination of the two rotations, 0.(04) and leaves the point C unmoved:
consequently, if there is a motion of a point on the sphere arising from the
combination of the given two rotations, then the third, resultant symmetry element
must pass through C, 0 and C.
Consider next the motion of the point A under the same two operations, The
rotation 0.(04) leaves point A unmoved: the rotation maps A on to A', where
ABC = A' B C = A' is, thus, the image of A in the plane 0 Be. In the spherical
triangles ABC and A'BC, ABC = A' B C = AB = A'B, and BC is common to
both triangles. The triangles are congruent, so that A CB = A' CB. Let these angles
be y/2; then the anti clockwise rotation y, about OC, maps A, along arc ABA', on to
A', Again, we consider Figure A3.2: under rotation o.(A), about bOb', point b is
invariant, whereas the rotation about eOe' moves b to b', We may write the
result symbolically as
o.(A) = y(C), (3,15)
which means that a rotation ex. in one sense about a symmetry axis OA followed by a
rotation in the same sense about an intersecting symmetry axis OB is equivalent to
a rotation y in the same sense about a mutually intesecting symmetry axis OC (or
clockwise about OC), where OA, OB and OC form a righthanded set of axes.
We can use triangle ABC to solve for the angles a, band c between the three pairs
of symmetry axes OB OC, OC 004, and OA OB; it is the reflection of triangle ABC
in the plane AOB. The solution follows the equations for the polar triangle
[Appendix 3, (A3.11) and its cyclic permutations], and the relevant portion of
Figure 3.4 is shown in Figure 3.5. We know that a (= 24), P(= 2 B) and y (= 2 C)
can take only the values 360° (0°), 180°, 120°,90° and 60°, corresponding to n = I,
2,3,4 and 6 in Cn.
Sec. 3.3] Defining, deriving and recognizing point groups 51
(ii) The value of 360° for 0., pand y is ignored, because it corresponds to the
trivial onefold rotation, or identity;
(iii) Since we need only the number of combinations of symmetry elements,
permutations are ignored so that only those solutions for 0. = 180°, 120°,90°
and 60°, with Ps 0. and y S; p, are required;
(iv) Solutions for which one or two of a, band c are zero are ignored, because they
correspond to a dimensionality in the problem of less than three.
B
A
S/2
c
P/2
Fig. 3.5 Spherical triangle ABC, to be solved for a, band c
Subject to these conditions, the six nontrivial results listed in Table 3.2 are derived.
In interpreting this table, we recall from Euler's construction that 0., ~ and y refer,
in order, to the anticlockwise rotations about the symmetry axes OA, OB and OC',
with a, b and c being the angles between the pairs of axes OB OC', OC' OA and OA
OB, respectively. Thus, in type (e), for example, we have two C
2
axes (0., P) with a
C
4
axis (y) normal to them, the angle c between the C
2
axes (OA and OB) being 45°.
Figure 3.6 illustrates the relative orientations of the symmetry axes, and the
stereograms show the effect of the symmetry operations on a typical point or vector
in an object ofthe corresponding symmetry. In the stereograms the vertical direction
(the normal to the stereogram) is the z axis and, except for Figure 3.6(h),
corresponds to the rotation axis of highest degree in the group. The y axis is the left
to right direction, and the x axis is perpendicular to both y and z. In Figure 3.6(h),
the x, y and z axes are C
2
symmetry axes, with C
3
axes along the bodydiagonal
directions of a cube; in Figure 3.6(i), the x, y and z axes are each C
4
symmetry axes
with C
3
axes again along the cube diagonals. Where are the C
2
axes in this
example?
In those groups for which there is a single axis of threefold or sixfold symmetry,
the orthogonal reference axes do not all coincide with the symmetry axes. However,
in studying crystal symmetry, it is conventional that the crystallographic reference
axes are taken along the directions of the symmetry axes, and we shall consider this
situation more fully in Chapter 8.
52 GrOU)l Theory and Point Groups [eh.3
Table 3.2 Results following from Euler's construction
Type «/deg Wdeg yldeg aldeg bldeg c1deg
d) 180 180 180 90 90 90
e) 180 180 90 90 90 45
f) 180 180 120 90 90 60
g) 180 180 60 90 90 30
h) 120 120 180 cos" (11...)3) cos" (1/...)3) cos" (1/3)
i) 90 180 120 cos"(...)6/3) cos" (1/...)3) 45
3.3.2 Building up the point groups
Now that we have determined the angles at which C, symmetry axes may intersect,
we can list the point groups corresponding to the types given in Table 3.2. For types
(d) to (i) they are, in order D
2
, D
4
, D
3
, D
6
(D, dihedral), T (tetrahedral), 0
(octahedral).
We explore now the combinations of C
2
and S!, but before we commence this
analysis we note the following general combinations, which may be deduced readily
either by application of (3.1) under multiplication, or with stereograms:
(Proper rotation) (Proper rotation) = Proper rotation
(Proper rotation) (Improper rotation) =Improper rotation
(Improper rotation) (Improper rotation) = Proper rotation
For type (d) in Table 3.2, the combinations of mutually perpendicular C
n
and 8
1
axes listed in Table 3.3 are permitted. The first entry in Table 3.3 lists three
mutually perpendicular twofold axes, and the pointgroup symbol for this
combination is D
2
, which we have already noted (Figure 3.6). Next we replace two
(Why not just one?) C
2
axes by S\ axes. We have seen that 8
1
is equivalent to a a
reflection plane normal to the direction of the SJ axis, and we have actually
considered this combination already in Section 3.2.3; it corresponds to point group
C
2v
. No other combinations are possible for type (d). However, we must always
consider if we have formed a group in each type that contains a centre of symmetry,
that is, it includes the operator i. Neither D
2
nor C
2v
is centrosymmetric, so now we
combine the operation i with D
2
, giving the partial group D
2h
{E, C
2
(z), C
2
(y), C
2
(x),
i, ...}. We know already that iC
2
is equivalent to a a plane normal to C
2
: thus, we
have further the operators a(xy), a(zx) and a(vz) perpendicular to C
2
(z), C
2
(y) and
C
2(x),
respectively. No new operators are produced by any other combinations
within this group: thus we obtain the character table below. We see that this point
group is Abelian (all pairs of symmetry operators commute) and its order is 8. Its
symbol, D
2h
, shows that it can be obtained from D:! by combining a reflection plane
normal to a C
2
axis in D:!. This result may be confirmed by comparing the
stereograms for D
2
and D
2h
in Figure 3.7. The combination of i (or ah) with the
Sec. 3.3]
Defining, deriving and recognizing point groups
53
45°
+0
0
d
e
f
9
h
Fig. 3.6 The permitted angles between rotation axes C;
54 GroUI) theory and point groups [Ch.3
Table 3.3 Permitted combinations of C
2
and SI for type (d)
OA (x) axis OB (y) axis OC' (z) axis Pointgroup symbol
C
2
C
2
C
2
D
2
s, s, C
2
C
2v
D
2h
E C
2
(z) C
2
(y) C
2
(x) cr(xy) cr(zx) cr(yz)
E E C
2
(z) C
2
(y) C
2
(x>: cr(xy) cr(zx) cr(Yz)
C
2
(z) C
2
(z) E C
2
(x) C
2
(y): cr(xy) cr(Yz) cr(zx)
C
2
(y) C
2
(y) C
2
(x) E C
2
(y): cr(zx) o'(pz) cr(xy)
C
2
(x) C
2
(x) C
2
(y) C
2
(z) E o (vz) cr(zx) cr(xy)
................ ~ ( ~ y j ..
.'cr(zx)""(j(Vi)'
E C
2
(z) C
2
(y) C
2
(x)
cr(xy) cr(xy) cr(vz) o'(zx) C
2
(z) E C
2
(x) C
2
(y)
cr(zx) cr(zx) cr(vz) cr(xy) C
2
(y) C
2
(x) E C
2
(z)
cr(yz) cr(yz) cr(zx) cr(xy) C
2
(x) C
2
(y) C
2
(z) E
symmetry elements of D
2
introduces all remaining symmetry elements of D
2h
. If we
repeat this exercise with C
2v
• we find that its combination with i (or crh) again
produces D
2h
. These results may be summarized by the scheme
+i or rr..
~
Direct products of groups
We may express these relationships neatly in terms of a direct product of groups,
either D
2
or C
2v
with Cj . The group multiplication table for D
2h
(above) may be
m
\±]
(a) (b)
Fig. 3.7 Stereograms tor point groups (a) D
2,
and (b) D2h: the introduction of the centre of
symmetry into D21eads to mirror planes perpendicular to all C
2
axes ofD2.
divided into quadrants, that outlined in the table being the group multiplication
table for D
2
. A direct product of D
2
and Cj is obtained by forming all possible
products between the symmetry operations of the two groups, which we may write as
D
2
(8) C, = D
2h
or, more conveniently
(3.16)
Sec. 3.3] Defining Point Groups 55
where the direct product symbol 0 implies all possible products under
multiplication between the symmetry operations of O
2
and i. It is not difficult to see
that the following direct products also lead to point group 02h:
O
2
0 ah = 02h
C
2V
0 i = 02h (3.17)
C
2v
0 ah = 02h
C
2
in the third equation (3.17) acts in a direction normal to ah (see also Section
3.2.4).
We consider one more example of pointgroup derivation from the data in Table
3.2, namely type (f), The axes OB and OC' correspond to the reference axes y and z
respectively, whereas the x axis lies between two C
2
axes, as shown in Figure 3.8a.
Although only three symmetry axes were needed in Euler's construction, a C
2
axis
normal to a C
n
axis leads to a total of n C
2
axes that are equivalent under the
symmetry C; Table 3.4 indicates the permitted combinations of one C
3
axis with C
2
and SI axes. In point group 0
3
, there are three C
2
axes in the xy plane, normal to the
C
3
axis (z) and related by it. The group may be written formally as 0
3
{E, C
3
, C:i ,
C
2
, C
2
" Cs}; its order is six, and the group multiplication table is easily
constructed. The stereogram in Figure 3.8a illustrates this point group; it appears
also among the six unique solutions in Figure 3.6.
If we replace the C
2
axes by SI axes then, because the Sl axes are normal to the C
3
axes, the symmetry planes to which they are equivalent are vertical (3a
v
) and
intersect in the C
3
axis. Thus, we have the group
C
3v
{E, C
3
• C:3 , a v, a v , a ~ }:
its order is 6, and its group table has been given in Section 3.2.5. Each of the point
groups O
2
and C
3v
combines with i to form D
3d
:
+i
(
The stereograms in Figure 3.8 illustrate these point groups and their
interrelationships.
In this way we may continue to derive the remainder of the thirtytwo
crystallographic point groups: we would find that no rotoreflection axis other than
SI is needed in this derivation; the other permitted S; axes emerge during the
Table 3.4 Point groups derived from type (f)
OA axis OB (v) axis OC' (z) axis Point group symbol
56 Group theory and point groups
> OY •
Y axis
1X ax t e
[eh.3
(b)
Fig. 3.8 Stereograms to show point groups (a) D3, (b) C3vand D3d; D3d may be formed from
D3 or C3v by direct product with Cj ••
derivation. A summary of the crystallographic point groups, together with the two
groups for cylindrical symmetry (linear groups), is provided in Table 3.5. A
program, EULS (EULH in the HermannMauguin notation), is available on the
Internet Web site www.horwood.net/publish (from where further user directions are
obtainable) that leads the user through the various stages of Euler's construction as
discussed above; it considers also certain noncrystallographic pointgroup
symmetries. The reader is encouraged to make use of this facility.
Table 3.5 Point groups and their symmetry operations
Group Operations
C
n
: One nfold (proper) rotation axis
C
1
E
C
z
E, c,
C3 E, C 3 " ' C ~
C
4
E, C
4
C
Z
C ~
C
s
E,Cs C; C ~ ... ct
C
6
E, C
6
C
3
••• C
Z
... C ~ ... C ~
C.: One mirror symmetry plane (a)
c, E, a
Cj : One point of inversion (centrosymmetry)
Sec. 3.3]
c. E, i
Defining Point Groups
S, : One nfold rotoreflection axis (n even)
57
54 E, S4.. ,S2."S
56 E, C3... C i ...8
6
... 8 , i
C
nv
: One C, axis and n vertical c, planes intersecting in C
n
C
2v
E, C
2
, 20
v
C
3v
E, C
3
C i , 30
v
C
4v
E, C
4
C
2
... C , 20
v
, 20
d
C
sv
E, 2C
s
2C; , 50
v
C
6v
E, C
6
C
3
... C
2
... C , C , 30
v
, 30
d
C
nh
: One C, axis and one 0h plane normal to C«
E, C
2
, i, 0h
C
3h
E, C3 ah
C
4h
E, C
4
C
2
C 8
4
... 5 . i, 0h
C
Sh
E, C, C; C C ... S5 5 ...8; , 0h
C
6h
E, C
6
C
3
C
2
... C 3 ... C 6 8
6
... 8
3
S 3 ... 8
6
, l, 0h
On: One C, axis and n C
2
axes normal to it
E,3C
2
E,
E, C4 C
2
... C , 2C , 2C
E, 2C
5
2C ... 5C
" 5 • "
E, C6... C
3
... C
2
... C '3 ... C 6' 3C 2, 3C 2
0nh: As On ' plus one (horizontal) 0h plane normal to C;
E, C
2
(z), C
2
(y), C
2
(x), i, o(xy), o(zx), o(yz)
E, C
3
C S3 S , 3C '2' ah, 30
v
E, C
4
C
2
C S4... S , 2C , 2C , i, 0h, 20v, 20
d
E, 2C
s
2C ... 2S... 2S ... 5S , 0h, 50v
2 5 "S'" •
E, C
6
... C
3
... C
2
... C 3 ... C 6 ... 56... 5
3
...5'3 ... 5
6
, 3C 2' 3C 2' I, 0h, 30v,
30
d
Ond : As On, plus n vertical (dihedral) ad planes intersecting in Cn
58 Group theory and point groups
1 '
E, C
Z
••• S
4
S 4, 2C 2' 2ad
E, C3.•. ci ,3C'2 .i, 3ad
E, 2S
8oo
.2C
4°o
.s.. .2S R , 4C ,4ad
Cubic groups: T, tetrahedral; 0, octahedral.
[eh.3
T E, 4(C
3
• ooC i), 3C
z
r, E, 4(C
3.ooC
i ",S6°o' S 3C
z
. i, 3ah
r, E, 4(C
3°o'
C i), 3(C
2
. ooS4°o'S 1)6 a d
o E, 4(C
3°o'C
D, 3(C4oo.Czoo.
C 1). 6C 2
0h E, 4(C
3°o'C
i oo,S6°o'S 6), 3(C4oo.CZoo. C1.·S4oo ,S1). 6C 'z, i, 3ah, 6ad
Coov : One C" axis and an infinity of a
v
planes intersecting in Coo
D
ooh
: As C
oov,
plus one ah, plane normal to Coo
D
ooh
E, .ooC ... S ... S ooC ,i, ooa
v
Notes on Table 3.5
1) Symmetry operators linked by the dotted line ... act collinearly.
2) Avertical symmetry plane is designated ad if it bisects the angle between twofold
axes that lie normal to the principal C
n
axis. In point groups C
4v
and C
6v
, the
labelling of the ad planes is not strictly consistent with this rule, but the notation
is general [lZ
l
.
3) In point group D
4
, the symmetry element C
2
' lies along the x axis and C
2
"
between x and y; in D
6
, C is along y.
4) In point groups D
4h
and D
6
" . the o, planes contain the symmetry elements 2C ,
and ad the elements . Strictly. all planes are ad type but the conventional
notation is used here.
5) In the linear point groups C
oov
and D",h, represents an arbitrary angle of
rotation.
6) The order of symmetry operations listed here will not necessarily be the same as
that in the corresponding character tables.
7) The pointgroup symbols C. and C, are preferred over S, and Sz.
8) Of the five cubic point groups, Td and 0" are of particular significance in
chemistry.
9) The unprimed symbol C
z
refers to an operation along the z axis, or the x, y and z
axes in the cubic point groups.
Sec. 3.3] Defining Point Groups
59
10) The symbols C
2
, and C
2
" refer to different forms (q.v.) of C
2
operations, n of
each, that are symmetryrelated under the principal C
n
operation. The symbols
C
2,
C
2
" C
2
" are used to indicate the n C
2
axes in one and the same form.
II) The parentheses in the cubic groups include operators with a common
multiplying factor, but which are not necessarily of the same symmetry class.
Thus, in r, 4(C
3
•.. C ~ ) leads to the class 8C
3
, whereas in Oh 4(C
3°o'C
~ 00 .S6... S ~ )
leads to the classes 8C
3
and 8S
6.
3.3.3 Federov and Plato solids
Federov showed[62j that there are only five polyhedra, each type of which can be
packed in one and the same orientation to fill space completely. Figure 3.9
illustrates the Federov solids; they are also WignerSeitz cells (q.v.), derived from
Bravais lattice unit cells:
Federov solid
Cube
Rhombic dodecahedron
Cube + octahedron
Hexagonal prism
Elongated rhombic
dodecahedron
Crystal form/s
{100}
{llD}
{100} + {Ill}
{l0 1 O}
{l00} + {lII}
Lattice unit cell
Cubic?
Cubic I
CubicF
Hexagonal R
hex
Tetragonal I
If the program EULS (or EULR) has been used in studying Euler's construction, it
would have been noticed that, although the program extends the discussion given
here to include the noncrystallographic rotation axes C
s,
C
7
and Cg, no point groups
emerged for which there were intersecting rotation axes of degree greater than 5, as
in point group I, for example. This result is related to the existence of only five
regular solids, the Plato solids, that is, those with regular polygonal faces, and
among which the maximum proper rotation axis found is C
s:
a regular polygon has
equal sides and equal angles between successive sides.
(a) (b) (c) (d) (e)
Fig. 3.9 Federov solids: (a) cube, (b) rhombic dodecahedron, (c) cube + octahedron, (d)
hexagonal prism, and (e) elongated rhombic dodecahedron. The cube is also a regular, Plato
solid.
The Plato solids may be determined from the following argument. Consider a
regular polygon with p sides, and let q such polygons form the comer of a
polyhedron. Since the internal angle of a polypgon is [90(2p  4)/p]0 and the sum
of the angles formed by the faces at any comer must be less that 360°, it follows that
q(2p  4)/p < 360/90, (3.18)
60 GrOUI) theory anti point groups [eh.3
which simplifies to
l/q + lip> \12. (3.19)
Euler showed
l13
] that the numbers of faces f, edges e and corners c of a polyhedron
are related by the equation
c +f= e + 2. (3.20)
Since, p and q must each be greater than 2, the only values of p and q that satisfy
inequality (3.19) are those listed in Table 3.6. The less familiar pentagonal
dodecahedron and the icosahedron are shown in Figure 3.10, and both exhibit C
s
and S\o symmetry axes.
(a) (b)
Fig. 3.10 (a) Pentagonal dodecahedron, (b) Icosahedron
Table 3.6 Values for p and q in (3.19), and the Plato solids
p,q e
f
c Plato solid Point group
3,3 6 4 4 Tetrahedron T
d
3,4 12 6 8 Cube
°h
4,3 12 8 6 Octahedron
°h
3,5 30 12 20 Pentagonal I
h
dodecahedron
5,3 30 20 12 Icosahedron I
h
These two solids are related to each other in the same way as are the cube and
octahedron, that is, by an interchange of the numbers of faces f and corners c. The
3,5 and 5,3 solids have the same symmetry, and their analyses are summarized in
Table 3.7.
From the symmetry axis SIO there are the operations E, 5
10
, 5 ~ o = C
s,
5 fo , 5 to =
c ~ , 5 io =i, S fo = 5; , S io , S fa = C ~ and Sio ;from Cs we obtain E and C 5 (n
= 14), all included with the SIO operations.
From S6 we obtain the symmetry operations E, 56, 5 ~ = C
3
, S ~ =i, S: = C ~
and S ~ : under C
3
we have the operations E, C
3
and C ~ , which are included with
the S6 operations. There are also fifteen C ~ operations and fifteen a operations in
each solid.
Sec. 3.3] Defining Point Groups 61
Table 3.7 Analysis of the pentagonal dodecahedron and icosahedron
Symmetry element Orientation of symmetry element
Pentagonal dodecahedron Icosahedron
Six SIO through:
Six C
s
collinear:
Ten S6 through:
Ten C
3
collinear:
Fifteen C
2
bisecting:
Fifteen cr containing:
centres of opposite pairs
of pentagonal faces
with SIO
opposite vertices
with S6
pairs of
opposite edges
two C
s
and two C
2
opposite vertices
with S,
centres of opposite
trianglar faces
with S6
pairs of
opposite edges
two C
s
and two C
2
If we analyse these data in the customary manner, we would deduce the following
symmetry classes for the pentagonal dodecahedron and the icosahedron: E, 12C
s,
12C; , 20C
3
, 15C ~ , i, 12S
10
, l25?o, 205
6
, 15cr. The point group is known as I
h
and its order is 120. If we excise all reference to the centre of symmetry, that is, all
8
10,56
, cr and i, we obtain the classes E. l2C
s,
12C ~ , 20C
3
, 15C ~ , which relate to
the pure rotation subgroup I. We shall not meet examples of point groups I and I
h
in
our study, but they are encountered with some molecules of biological interest.
3.3.4 Practical recognition of point groups
In the scheme for practical pointgroup recognition to be described here, molecules
and crystals are divided first into four groups depending upon the presence of a
centre of symmetry, or a mirror plane, or a centre of symmetry and a mirror plane,
or neither of these two symmetry elements, leading to Table 3.8.
The recognition of a centre of symmetry or of a mirror plane is very
straightforward: for a centre of symmetry, place the given model on a flat surface;
then, if the plane through the uppermost atoms (in the case of a molecular model) or
the uppermost face of the crystal (in the case of a crystal model) is parallel to the
supporting surface, a centre of symmetry is present in the model.
If a mirror plane is present, it divides the model, conceptually, into halves that are
related as an object is to its mirror image, the well known righthandslefthand
enantiomorphism. It is suggested that the reader examine these simple rules with
models of SF
6
(or a cube) and CH
4
(or a tetrahedron), or other examples. A correct
identification at this stage is important: it places the model into one of types IIV,
shown by Table 3.8 and Figure 3.11.
Further study concentrates on the nature of the principal symmetry axis, the
number of them, if more than one, the presence of other mirror planes or twofold
axes and so on, according to the scheme illustrated in Figure 3.11. It will be
apparent that this scheme resembles a flow diagram of a computer program'!".
Indeed, the procedure can be carried out with the program SYMS which is accessible
62 Group TheoryandPoint Groups [eh.3
Further study concentrates on the nature of the principal symmetry axis, the
number of them, if more than one, the presence of other mirror planes or twofold
axes and so on, according to the scheme illustrated in Figure 3.11. It will be
apparent that this scheme resembles a flow diagram of a computer programl'"'.
Indeed, the procedure can be carried out with the program SYMS which is accessible
tIl (II)
" I n > 17 1.+1 C I n )0 11 101 C_I
Yo. No II r e e I'
.nd n '=" 4.7 +i T ,
'.'" 'I I
La'" i II
 I
I I
I D
I ae
I
!
I
I
I
ur n
...
56
(!V)
n e J I
::\, 0 4? '0
T
' . Th'
!fa Ye'S
h
(J'h. .1. c » No CI
?
"'
(J'h .l C? MOl
n
Yo.
l:d
(I)
w
w
......
=
tll
:l
= ...
=
IJCl
"l:l
Q
a
j
'"
Fig.3.11 Block diagram of the pointgroup recognition scheme embodied in the program SYMS (and SYMH). The point groups Coov and Dooh fit
the scheme under types (Il) and (IV), respectively.
w
64 GrOUI) theory and point groups [eh.3
Table 3.8 Pointgroup recognition scheme: the basic divisions
Type I Type II Type III Type IV
C
1
C
2
c, C
2v
c, 56 C
2h
C
4h
C
3
C
4
C
3v
C
4v
C
6h
~ ~ ~ ~ ~
~ ~ ~ ~ ~ ~
D
4
D
6
D
2d
r, r, o,
T 0 Caw D
ooh
under the WWW reference already quoted; a key to the link between a 'model
number' and its point group is also provided.
For best results the model should have been studied carefully along the lines
indicated'" before using the program. If an error is made in the deduction process,
the program returns the user to the point in the scheme at which the error has been
made. Up to two such returns are allowed before the program offers a suggestion for
alternative action.
The thirtytwo crystallographic point groups are illustrated in Figure 3.12, using
the traditional stereogram notation. The two diagrams for each point group show the
symmetry elements, and the general equivalent positions that are related by the
pointgroup symmetry. General positions do not lie on any symmetry element:
special equivalent positions exist on symmetry elements, and the number of them
for a given point group is a submultiple of the number of general positions. For the
point groups C
2
, C, and C
2h
, the two diagrams given relate to the choice of the
twofold axis: it may be taken along z, which is conventional in molecular symmetry,
or along y, which is the universal crystallographic convention. Table 3.9 provides a
comparison of pointgroup symbols in the Schonflies and HermannMauguin
notations, with example compounds for each group.
Sec 3.3] Defining, deriving and recognizing point groups 65
0 CD8
ffiEB
C
1
(l) C
2
(2)
C
4
(4)

00
ffiEB
c, (m(=2))
8
4
(4)
CD CD8
ffiEB
< (1)
C
2 h
(2im) C
4h
(4Im)
CDS
CDi
i
\
ffi ,:r,
111
a • _¥t
a • "'1/
• • a
a ..........
C
2
(2) D
2
(222) D
4
(422)
CDCD CDEB ffi®
C
s
(m) C
2 u
(mm2) C
4 v
(4mm)
 
a a. • \(IY
I

D
2d
(42m)
,
wEB
CDri\
€B
I
00 11.. I
I
o 0 I" \
ttt
o 0
i
00 \....1/
00 I
....
C
2 h
(21m) D
2h
(mmm) D
4h
(4Immm)
Fig. 3.12 Stereograms of the 32 crystallographic point groups: the 1st and 2nd settings for
monoclinic crystals correspond to the unique, twofold axis along z and y, respectively. Both
symmetry notations (Table 3.9) are used in this figure.
66 Group theory and point groups [Ch.3
®
I ' \  ~
. ·.J.
o. 0 \j \,J
D
3
(32) 
®@
.. @
• • • •
.. :. .: .
• • • •
c
6 u
(6mml
Sec. 3.3] Defining, deriving and recognizing point groups 67
Table 3.9 Synunetry notations and example compounds
Schonflies HermannMauguin Example or possible example
Cj I CHBrCIF, bromochlorofluoromethane
~
2 H
202,
hydrogen peroxide
C
3
3 H
3P04,
phosphoric acid
C
4
4 (CH3)4C4, tetramethylcyclobutadiene
C
6
6 C
6(CH3)
~ , pentamethylcyclopentadienyl

C, I C6HsCH2CH2C6Hs, dibenzyl
C. m C
6H3Ch,
1,3,5trichlorobenzene

[H
2P04
L dihydrogen phosphate ion S4 4

[Ni(N0
2)6(
, hexanitronickelate(II) ion S6 3
C
2h
21m CHCl=CHCI, transI,2dichloroethene

C
3H3N3(N3
h, 1,3,5triazidotriazine C
3h
6
C
4h
41m [Ni(CN)4f, tetracyanonickelate(II) ion
C
6h
61m C
6(CH3
k hexamethylbenzene
C
2v
mm2 C ~ s C I , chlorobenzene
C
3v
3m CHCh, trichloromethane
C
4v
4mm [SbFsf , pentafluoroantimonate(V) ion
C
6v
6mm C
6(CH2Cl)6,
hexachloromethylbenzene
O
2
222 C
8H14,
cyclooctaI,5diene
0
3
32 [S206f, dithionate ion
0
4
422 Co(H
20)4Cb,
tetraaquodichlorocobalt
0
6
622 C
6(NH2)6,
hexaminobenzene
02h
mmm C
6H4C12,
1,2dichlorobenzene
03h
6m2 [C0
3f,
carbonate ion
04h
4
[Aufira]", tetrabromoaurate(III) ion mm
In
06h
6
C
6H6
, benzene mm
m
02d
42m ThBr4, thorium tetrabromide

C
6H12
, chair cyclohexane
03d
3m
T 23 C(CH
3)4,
2,2dimethlypropane
T
h
m3 [CO(N0
2
)6f , hexanitrocobaltate(III) ion
T
d
43m CH
4,
methane
0 432 C
8(CH3
) 8, octamethlylcubane
Oh
m3m SF6, sulfur hexafluoride
Noncrystallographic point groups
8
8
, sulfur
C
S(CH3
) ; , pentamethylcyclopentadienyl
CsHsNiNO, nitrosylcyclopentadienylnickel
(CsHshRu, biscyclopentadienylruthenium
(CsHshFe, biscyclopentadienyliron
HCI, hydrogen chloride
CO
2
, carbon dioxide
68
D
4d
82m
C
s
5
c; 5m
D
Sh
10m2

D
Sd
5m
c., om
D
roh
odm
Group theory and point groups [Ch.3
PROBLEMS 3
3.1 Which pairs of operations C
2
, C
3
, rr and E commute?
3.2 Construct a group multiplication table for (a) C
2h
and (b) D
2d
. Is either of these
groups Abelian?
3.3 Construct a multiplication table for the cyclic group 6{E, A, B, C} of order
4, using the relations A = r, B = ?, C = r
3
. Which operation, other than E, is
its own inverse?
3.4 Figure P3.1 is a stereoview of the dithionate ion, as seen along the ss bond.
(a) Determine the point group of this species. (b) Construct a group multiplica
tion table for this point group. (c) Determine the subgoups of this point group.
(d) Which, if any, ofthe subgroups is invariant to the point group of the species.
3.5 By means of similarity transformations, or otherwise, show that the three cr
operations in C
3v
fall into one symmetry class.
Fig. P3.1 Stereoview of the dithionate ion, along the SS bond.
3.6 From a consideration of group multiplications tables, show that the point group
54 cannot be obtained from any combination of symmetry operations, whereas
56is equivalent to a certain combination. Then, determine this combination.
3.7 What point groups are formed by the direct products of (a) D
4
and i, (b) C
4
and
cr(xy), and (c) i and cr.
3.8 What point groups may be developed from type (e) in Table 3.2'1
3.9 Use stereograms to show that C
4v
combined with i leads to D
4h
.
3.10 Determine the point groups of each of the following chemical species from
their stereoviews:
Problems
a
b
c
69
70
Group Theory and Point Groups [eh.3
d
e
f
Fig P3.2 Stereoviews of the structures of six chemical species: (a) l,3 ,5triazidotriazine; (b)
chlorobenzene (c) cyclohexane (chair); (d) methane; (e) octafluorotantalate(V) ion
(square antiprism); (f) hexachloroplatinate(IV) ion.
Problems 71
3.11 Show that a group consisting of the unique members E, A, B, C, D and F
cannot have any member more than once in any column or row within the
table.
3.12 Show that if any two members P and Q of a group satisfy the relation P =
o'ro. then P and Q commute.
3.13 Howmany groups may be constructed, and what are their types, for (a) order 4,
and (b) order 5? Draw up group multiplication tables and list any members
that are their own inverses.
3.14 Which of the symmetry operations of the point group of the dithionate ion
(problem 3.4) are conjugate one with the other?
3.15 Is it true or false that the following pairs of symmetry operations commute?
(a) C, ... C n ~ (b) C, and i; (c) cr(xy) and cr(vz),; (d) C
2
(z) and C
2
(y); (e) C, and
crh; (f) C
4
(z) and C
2
(x); (g) S, (n even) and i.
3.16 Comment on the equation cr
b
C
4
= 8
4
in its relation to 54, the point group for
C ~ , or a regular tetrahedron.
3.17 Use the pointgroup symbol D
4h
to show the power of the Schonflies notation.
Take the crh plane normal to the C
4
axis and the C ~ axes in the c plane (along
x and y), all indicated by the symbol, and show by means of a stereogram, or
otherwise, that all other symmetry elements of the group are introduced.
3.18 Show that the members ma (m = CXJ, ... 1, 0, 1, ...CXJ) form a group under a
certain law of combination, and state that law.
3.19 This problem and the next are designed for use with the program SYMS (or
SYMH). The numbers in parentheses are the model numbers for use with the
program. Determine the point group for (a) a regular tetrahedron (23), (b) a
tetragonal pyramid (87), and (c) a hexagonal prism (33). Give the results in
both the Schonflies and the HermannMauguin notations.
3.20 Determine the point group for the species (a) cyclohexane in the chair form
(40), (b) 1,2,4trifluorobenzene (71), and (c) trichlordeuteromethane (42). Give
the results in both notations.
3.21 Draw four irregular but identical quadrilaterals on a thin card. Cut them out
and arrange them to form a symmetrical figure. What is the pointgroup
symmetry of the resultant figure?
3.22 Figure P3.3 can be used to construct a model of a rhombic dodecahedron, a
Federov solid. Make an enlarged photocopy of the figure; a second sheet of A4
paper glued to the back of the photocopy adds a useful rigidity. Cut out the
figure, lightly score the dotted hingelines and fold all portions in the same
sense. With a quickdrying glue, attach the flaps to the faces, flap A to face A,
and so on. What is the point group of the model? If you are using the program
SYMS (or SYMH) for pointgroup recognition, this model can be numbered 10.
72 GroUI) theory and point groups [eh.3
H
D
,
,
,
,
,
,
,
I
I
I
I
I
I
I
,
,
, ...... ~
~ : ~
I I
I I
I I
I I
I I
~ I I
: ~ '
. ,
, ,
, ,
, ,
, ,
">4
B
F
E
c
I
I
J
I
I
I
I
I
[::>
: _ "
, ,
, ,
, ,
.  ?' \
I , , ,
:<j/ " " ' ~
/'" j'" A
\"('" (B:/
" .
',  ~ ' _..'
Fig. P3.3 Model of a rhombic dodecahedron
4
Representations and character tables
Our characters are the result ofour conduct.
Aristotle (384322 BC): Nicomachean Ethics
4.1 INTRODUCTION: WHAT IS A REPRESENTATION
A representation of a point group may be given through a set of matrices, each of
which corresponds to a single symmetry operation in the group. In effect, we give
symmetry operators such as C
3
an algebraic significance, so that we work in
numerical terms and reach precise conclusions. In this way, we link molecular
symmetry with practical considerations such as whether or no a given chemical
species is active in the infrared spectral region.
4.1.1 Representations on position vectors
One procedure for obtaining a representation is through the effect of symmetry
operations on a position vector in a body. We have laid the foundation for this
method in the development of (2.57). We note that that matrix which represents a
clockwise rotation about the z axis, by an angle 8, of a set of orthogonal reference
axes for a body, is applicable also to the rotation by the same angle of a point or
vector within the body but in the anticlockwise (positive) sense.
Ifp is the position vector from the origin of these axes to a point x, y, z, we write
p = xi +yj +zk, (4. I)
where i, j and k are orthogonal basis vectors of unit magnitude (unit vectors)
chosen along the directions of the x, y and z axes, respectively. This equation
contains a convention of which we must note. In extenso (4.1) is written
(4.2)
where the set of unit vectors is a 1 x 3 matrix, or row, and the set of coordinates
forms a 3 x 1 matrix, or column.
The (anticlockwise) rotation of the vector p about the z axis is governed,
following (2.57), by
74
Representations and character tables
[eh.4
or more concisely by
[
C ~ S ( O )
= sm(O)
a
 sin(O) OJ
cos(O) a
a 1
(4.3)
p' = D(R)p, (4.4)
where p' is the vector after rotation and D(R) stands for the matrix that is
representing the rotation R. We use the term Dmatrix (Ger. Darstellung =
representation) in order to distinguish it, strictly, from the symmetry operation
itself. For an operation C, about the z axis, normal to the xy plane, D(C
n
) is
obtained by substituting in (4.3) the value of eappropriate to the degree of rotation.
Matrices can be constructed in a similar manner to represent the symmetry
operations Sn, 0" and i (see also Appendix 13).
EXAMPLE 4.1. We find the coordinates of a position vector, initially at 0.1000, 0.2000,
0.3000 with respect to orthogonal axes, after an anticlockwise rotation of the vector, in the
xy plane, about the z axis by 60°. From (4.3), the matrix D(C
6
) becomes
1 V3
 0
2 2
V3 1
 0
2 2
0 0 1
whereupon we have
x' = 0.1(1/2) + 0.2(.J3/2) + 0.3(0) = 0.1232
y' = 0.1(.J312) + 0.2(1/2) + 0.3(0) = 0.1866
z/ = 0.1(0) + 0.2(0) + 0.3(1) = 0.3000
We use the water molecule, point group C
2Y
, for an example of forming a
representation by this method. Figure 4.1 illustrates the orientation of the reference
axes in this species; the x axis is normal to the plane of the diagram, at the oxygen
atom. The matrices that represent the symmetry operations in C
2y
are assembled in
(4.5): thus, for each symmetry operation R we have the corresponding matrix D(R)
representing that operation. Each matrix may be seen to be correct with the aid of
+z axis
I
I
I
AY";'
H
b
H
a
Fig. 4.1 Water molecule, H20: C
2
is along z, cry is the xz (vertical) symmetry plane and c ~
is the yz (molecular) plane. The hydrogen atom H. is referenced at a general position X, y, z.
Sec. 4.1]
[
10OJ
D(E) = 0 1 0
001
E
[
1 0OJ
D(cr
v
) = 0 1 0
001
What is representation
D(C
2
) = [ ~  ~ ~ I
o 0I)
C
2
[
10OJ
D(crv ' ) = 0 1 °
°0 I
75
(4.5)
Figure 4.1. For example, D(cr
v
) would convert a point x, y, z to x, y, z, which is
correct for a reflection across the xz plane passing through the point y = O. As we
have already expressed the combination of symmetry operations under
multiplication by equations such as (4.6), so we now add a numerical significance
through the Dmatrices in (4.7):
] = n! H
D(C
2
)
In extenso (4.7) becomes. by standard matrix multiplication,
[
1 0 0] [1 0 0
o 1 0 0 1 0
00100 1
D(cr,) D(cr:)
(4.6)
(4.7)
(4.8)
it shows that the effect of successive operations across symmetry planes
perpendicular to each other is equivalent to a twofold rotation from the initial
position (see Figure 1.4, Section l.l).
The set of matrices (4.5) is one representation of the symmetry operations ofC:!y,
and the set forms a group because it satisfies the group postulates in Section 3.2.1.
Equalities such as (4.7) mirror the group multiplication table, and we may
formulate a group multiplication table for the Dmatrices that is homomorphic with
the table for the symmetry operations themselves:
C:!, E C
2
cr,. cry D(C
2
, ) D(E) D(C
2
) D(cr
v
) D(cr:)
E E C
2
cry cry
D(E) D(E) D(C
2
) D(cr
v
)
D(cr:)
C
2
C
2
E cry c, D(C
2
) D(C
2
) D(E)
D(cr:)
D(cr
v
)
cry cry
0,;
E C
2
D(cry) D(a,) D(o:) D(E) D(C
2
)
cry
cry
Oy C
2
E D(cr:) D(cr:) D(a,) D(C
2
) D(E)
The Dmatrices are orthogonal (Section 2.5.3), so that the inverse of each matrix is
equal to its transpose: the matrices in this example are also symmetric, so that D(R)
= fj (R) =0
1
(R).
76 Representations and character tables
[Ch.4
4.1.2 Representations on basis vectors
We may use instead a set of orthogonal basis vectors. Consider the point group C
3v
,
of which the ammonia molecule is a well known example. Figure 4.2 illustrates the
trigonalpyramidal base of the ammonia molecule. The basis unit vectors are i, j
and k, where k is directed upwards from the plane of the diagram.
The operation C
3
rotates i and j to if and .if, respectively: operating then on if and
.if with cry leads to i" and .i". Operating on i and .i directly with cry" leads
immediately to i" and .i"; thus,
o.C, = cry"
C,«, = cry'
(4.9)
(4.10)
as we would now expect. It is straightforward to show, by simple geometry or from
matrix D(R) in (4.3) remembering that i, .i and k form a 1 x 3 vector triplet, that
if (= C
3
i) = (l/2)i + C·hl2).i, (4.11)
J' (= C
3
.i) ('h/2)i  .i/2, (4.12)
k
f
(= C
31<)
Ii. 4.13)
.
1(1'
I v
I
j
...
....
I
I
\ I
\ I ,,"'
\ I ,.,' i'
". '\ I: ,.'
........ ".
"'
'H
2
Fig. 4.2 Trigonalpyramidal base of the Nth molecule: C
3
lies normal to the diagram, and
the filled equilateral triangle is the conventional symbol for threefold rotation; i, j and k are
unit vectors, and k is invariant under all operations of C3v.
Sec. 4.1]
What is representation 77
From arguments similar to that just pursued for C
3,
we can obtain all six D
matrices for C3y. It is left as an exercise for the reader to show that the following
results may be obtained through Figure 4.2. It should be noted that the vector
coefficients on the righthand sides of (4.11)(4.13) appear as columns in (4.14).
We will call this collection of matrices in (4.14) the representation fl.
u
0
~ ]
[1/2 ';3/2
~ ]
D(E)
= 1
D(C )
=
v3/2 1/2
0
3
o 0
D(C
2
)
[ 1/2 ';3/2 0 ]
U
0
n
= v3/2 1/2 0
D(cry )
=
1
. (4.14)
3
001
0
[1/2
';3/2 0 ]
r1/2 ';3/2 0 ]
D(cry ' ) = V 3 ~ 2 1/2 0 D(cr
y
" )
= v3/2 1/2 0
o 1
001
It is possible to form another representation of C
3,
again using the ammonia
molecule as an example, this time in terms of unit vectors r, (NH
I
) , r2 (NH
2
),
and r, (NH
3)
along the three NH bonds, Figure 4.3. The C
3
axis lies along k
and the cry planes are orientated as in Figure 4.2, with cry as the i.k.r, plane and so
on. Then, we have
C r
=
r
],
3 1 2
Cr
=
r
3 2 3
Cr
=
r
3 3 1
cryrl =
r
]
1
cr
y
r2
=
r
3
crv
r3 =
r
2
(4.15)
(4.16)
These equations lead to two Dmatrices, and by following through this procedure
the remaining four matrices are readily obtained; the six matrices together form a
new representation, I'2:
78 Representations and character tables
[Ch.4
D(E)
=
=
=
a
1
a
1
a
a
1
a
a
D(C) =
3
a
a
1
a
a
1
a
1
a
(4.17)
It is reasonable to enquire if these two representations of C
3v
are equivalent.
Referring again to Figure 4.3, we see that the angles between the direction of k and
each of r., r2 and r, are equal, say a. Then the component of each bond unit vector
resolved along k is k cos(a) and, with reference also to Figure 4.2, we obtain the
equations (4.18), which may be solved for i, j and k.
rl == i sini«)  k cos(a)
r2 == 1'2i sin(a)  13 j sin(a)  k cos(a)
2
r, == l;2i sin(a) + 13 j sin(a)  k cos(a)
2
(4.18)
(4.19)
It is useful to make the substitution sin(a) == p and cos(a) == q, whereupon we obtain
the set of inverse equations:
i == (2."1  r2  r3)/(3p)
j = (r2  r3)/(p 13)
k == (r,  r2  r3 )/(3q)
We note en passant that the rl, r2 and r, vectors are not orthogonal:
r1 ·r2 == r2·."1 == r3·r\ == _p2/2 + q2 . (4.20)
Orthogonality is achieved only for p/q == tan(a) == ~ 2 , that is, when a == 54.74°, or
one half of the tetrahedral angle. However, for a given matrix D
2
(C
3
) from f
2
we
should be able to retrieve D
I
(C
3
) off, from the similarity transformation'P'
Sec.4.lJ What is representation
k
N
79
/
/
/
/
/
/
/ f
I I
H
3
~     ,  
,
" f
"f ____
" ...
.. 
HI
j
\
\
\
\
\
\
   J_ H
2
...
Fig. 4.3 Representation for C3v on the NH bond vectors in the NH3 molecule: i, j and k are
orthogonal unit vectors, and i, k and ri are coplanar, defining (iv.
Q,ID
2
(C
3)Q
= D
I(C3
) . (4.21)
D
I(C3
) and D
2(C3
) are taken from (4.14) and (4.17), respectively, and Q, from
(4.19), and Q.I are given by
2 a 1
p/2 p/2
3p 3q
P
1 1 1 1
a
pi3 pi3
(4.22)
Q =
3p p1/3 3q
Q =
2 2
,
1 
1 1
3p p1/3 3b
q q q
from which the result of (4.21) follows readily. In general, two representations of a
point group by matrices Da(R) and Dp(R) are equivalent if a matrix Q exists that
obeys (4.21) for all symmetry operations R of the given group.
4.1.3 Representations on atom vectors
We refer again to Figure 4.1 and imagine now three new sets of orthogonal vector
components x, y and z, originating one set from each atom in the molecule. We will
designate them x
o,
Yo, Zo for oxygen and x., Y., z, and Xb, Yb, z, for the two hydrogen
atoms. These sets of axes are conveniently, though not necessarily, parallel, and by
applying the symmetry operations of C:2v they lead to a representation consisting of
a set of four 9 x 9 matrices. For example, C
2
applied to the oxygen atom has the
general effect:
80 Representations andcharactertables
X 7X
o 0
Yo 7 Yo
z 7 z
o 0
[eh.4
whereas cry, the xz plane, acting on hydrogen atom H, leads to
x 7 X
a a
Proceeding in this way, we obtain the four matrices shown in (4.23)(4.26).
Application of the rules for matrix multiplication shows that these matrices
reproduce both the transformations listed above, and equivalent transformations for
the other hydrogen atom and other symmetry operations.
1 0 0 0 0 0 0 0 0
0 1 0 0 0 0 0 0 0
0 0 1 0 0 0 0 0 0
0 0 0 1 0 0 0 0 0
0 0 0 0 1 0 0 0 0
0 0 0 0 0 1 0 0 0
0 0 0 0 0 0 1 0 0
0 0 0 0 0 0 0 1 0
0 0 0 0 0 0 0 0 1
X
Xl
0 0
Y
yl
0 0
Z
Zl
0 0
X
Xl
a a
y =
yl
(4.23)
a a
Z
Zl
a a
X
Xl
b b
Yb
yl
b
Z
Zl
b b
D(E): X=9
1 0 0 0 0 0 0 0 0 X
Xl
0 0
0 1 0 0 0 0 0 0 0 y
yl
0 0
0 0 1 0 0 0 0 0 0 Z
Zl
0 0
0 0 0 0 0 0 1 0 0 X
Xl
a a
0 0 0 0 0 0 0 1 0
Ya
=
yl
(4.24)
a
0 0 0 0 0 0 0 0 1 Z
Zl
a a
0 0 0 1 0 0 0 0 0 X
Xl
b b
0 0 0 o 1 0 0 0 0
Yb
yl
b
0 0 0 0 0 1 0 0 0 Z
Zl
b b
D(C
2
) : X=1
What is representation Sec. 4.1]
1 0 0
0 1 0
0 0 1
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
1 0 0 0 0 0
o 1 0 0 0 0
0 0 1 0 0 0
81
x x'
0 0
y
yl
0 0
Z
Zl
0 0
X x'
a a
Ya
=
yl
(4.25)
a
Z
Zl
a a
X
Xl
b b
Yb
yl
b
Z
Zl
b b
1 0 0 0 0 0 0 0 0
0 1 0 0 0 0 0 0 0
0 0 1 0 0 0 0 0 0
0 0 0 1 0 0 0 0 0
0 0 0 0 1 0 0 0 0
0 0 0 0 0 1 0 0 0
0 0 0 0 0 0 1 0 0
0 0 0 0 0 0 0 1 0
0 0 0 0 0 0 0 0 1
X
Xl
0 0
Y
yl
0 0
Z
Zl
0 0
X
Xl
a a
Ya
=
yl
(4.26)
a
Z
Zl
a a
X
Xl
b b
Yb
y'
b
Z
Zl
b b
Each of these 9 x 9 matrices is blockfactored (see Section 2.5.5), and we can
multiply corresponding blocks together: taking the first block from each of D(C2)
and D(cr
y
) it is evident that similar results arise for all other pairs of corresponding
(4.27)
blocks. Thus, the sets of blocks themselves are also representations of C2y. The 9 x
9 matrices are said to be reducible, and the representations formed from the blocks
are termed irreducible representations of the group, which will be a subject of our
82 Representations and character tables
[Ch.4
main interest. Thus, the representation obtained from (4.23)(4.26) may be written
in terms of the traces, or characters, of the matrices as
~ I E C2 crv cr
v
f 3n I 9 1 3
where n refers to the number of atoms in the molecule, so that 3n indicates the total
number of basis vector components. By a procedure that we shall discuss shortly,
this representation may be reduced to the irreducible representations 3A1 + A2 +
2B) + 3B
2
. We discuss the notation for irreducible representations in Section 4.2.2;
for the moment, we treat them simply as labels for certain sets of characters. The
total number of irreducible representations is equal to the number of basis vectors
here, because these irreducible representations derive from onedimensional
matrices.
Unshiftedatom contributions to a representation
In the previous section, we showed how a representation I'3n could be generated
from the transformations of sets of orthogonal x, y and z vector components, one set
originating from each atom of a molecule. This type of representation is important
in studying molecular vibrations: we can deduce some general relationships
governing the contributions to the characters Xof the Dmatrices according to the
vector shifts under the symmetry operations of a given point group.
If a symmetry operation R shifts an atom, or one or more of its attached
orthogonal vectors, then the diagonal terms of the Dmatrix for the operation R
indicate its contribution to XR. Considering again the water molecule, we indicate
the contribution of an unshifted vector component by +I or 1 according as the sign
of the component remains the same or is negated; a shifted component contributes
O. Table 4.1 lists the results of this analysis.
We can make the process more general by working through the pointgroup
symmetry operators that we have met in our study of symmetry so far. From Section
2.2.3, a rotation operation C, about the z axis has the effect
[
cos(360In) 0
o cos (360In)
o 0
o
o
1
and the contribution to XR for an unshifted atom is [2 cos(360/n)O + 1]; for C
2
, n =
2, so that XC2 = I. In the case of reflection across a cr(xz) plane, we have the
equivalence of Sl alongy, so that the above matrix would become
[
cos(360In)
o
o
o
1
o
The I arises in the position shown because the axis of rotation is now y, and the
reflection across the xz plane changes the sign ofy. Thus, with n = I, we have
Sec. 4.1] What is representation 83
so that the contribution for an unshifted atom (VA) under this symmetry operation
is 1  1 + 1 = 1. Proceeding in this manner, we can draw up Table 4.2 for all
symmetry operations that we encounter in this work.
Table 4.1 Vectorshift contributions to XR in the water molecule
0 H H r
a b 3n
X y Z X
Y
z X y z
E 1 1 1 1 1 1 1 1 1 9
C 1 1 1 a a a a a a 1
2
cr
v
1 1 1 a a a a a a 1
cr
v
' 1 1 1 1 1 1 1 1 1 3
Table 4.2 General contributions to X,R for an unshifted atom in r 31/
R
X
R
R
X
R
C 1 C
3'
c
2
a
2 3
C
4'
c
3
+1 C
6'
c
5
+2
4 6
5
3'
52
2 5
4 '
53
1
3 4
5
55
a
o
+1
6'
6
i
3 E +3
EXAMPLE 4.2. We deduce a f311 representation lor the ammonia molecule, point group C3v.
From Figure 4.2 or 4.3 we determine the unshifted atoms under each operation of C3v and
then use Table 4.2 to obtain the contributions to X; we need consider only one symmetry
operation in each class, because all operations in one and the same class behave alike. Thus,
we find
Unshifted atoms
f31/
E
4
12
3o
v
2
2
We are not concemed with the reduction of this representation at this stage.
4.1.4 Representations on functions
Mathematical functions also may be used as a basis for generating representations.
For our purposes, the wavefunctions that define atomic orbitals are of particular
significance and will feature in subsequent chapters.
The p atomic orbitals may be written concisely as
84 Representations and character tables
[Ch.4
P
x
=
f(r)x/r
}
P
y
= f(r)y/r
P
z
f(r)z/r
Using polar coordinates (see Appendix 5), we have
P
x
= fer) sineS) cos(¢)
}
P
y
= fer) sineS) sin(¢)
P
z
= fer) cos(S)
(4.28)
(4.29)
where the radial componentj(r) is unaffected by the symmetry operations, because
the origin remains unmoved by the operations of a point group. We will determine
the Dmatrices for transformations under the symmetry C
3v
, that is, the operations
E, C
3
and G
v
• Reference to Figure A5.1 (Appendix 5), shows that e is invariant
under all operations of C
3v
. Under C
3
, is changed by +21£/3; thus, we have
sineS' ) = sineS)
cos(¢' ) = cos(¢) cos(2nI3)  sin(¢) sin(2n/3)
1
sin(¢) (4.30) = cos(¢) 
2 2
sin(¢' ) = sin(¢) cos(2nI3)  cos(¢) sin(2nI3)
!sin(¢)
V3
= +  cos(¢)
2 2
Hence,
=
2
1 V3
p  p'
2 X 2 y'
sineS) sin(¢)
2
(4.31)
= sineS) cos(¢)  !f(r)sin(S)sin(¢)
2 2
= (4.32)
In a similar manner we can show
Gvp, = .f(r) sin(fl) = Px
c.p, = j(r) sinCe) = P
y
Clearly Ep, = Px and Ep, = py , and we obtain the following matrices:
(
I 0) _2
o I XE  ,
(4.33)
(4.34)
Sec. 4.1] What is representation 85
(4.35)
(
1 0) <cr
v
=0
°1
(4.36)
o 1
Since the character for C ~ is the same as that for C
3
and those for cry' and cry" the
same as that for o ; the I'E (x, y) representation in C
3v
, using Px and pyas basis
vectors, becomes
~ E
f
E
I 2
If we consider also the pz orbital, it follows from (Appendix 5) that for all
operations of C
3v
P: = pz .
(4.37)
The matrix for each operation on pz is (I), so that XP = 1, 1, 1, which we will soon
recognize as a fully symmetric A1 representation. Reference to (4.14) shows that we
have obtained the two parts of blockfactored matrices such as
D(E) =
[
(4.38)
If we add the representation for pz to that for Px and Py, we obtain
E
3
f         '       ' 
as we found for the totality of (4.14). Referring to the character table for C
3v
(see
Appendix A11.1), we see that the angular functions sin(8) cos(<j» and sin(8) sine<j»
transform like x and y: thus, the p orbital with the eigenfunction proportional to
sin(8) cos(<j» is called p, and the p orbital with the eigenfunction proportional to
sin(8) sin(<j» is py
4.1.5 Representations on direct product functions
In a manyelectron problem, such as we shall meet later, a wavefunction may be
defined in terms of the product of a number of other wavefunctions:
(4.39)
where \III, \V2, ... may be s. p, d or other atomic orbitals.
We have seen in the previous section how individual orbitals may be labelled by
the irreducible representations to which they belong; for example, pz is labelled AI.
A product function is formed by the direct product of the irreducible
representations, and we illustrate the process with the character table for point
group T
d
:
86
Representations and Character Tahlcs [eh.4
T
d
E 8C 3C 65
6crd
3 2 4
A
1
1 1 1 1 1
A 1 1 1 1 1
2
E 2 1 2 0 0
T 3 0 1 1 1
1
T
2
3 0 1 1 1
For the product of any two of these representations, we form the direct product of
the characters for each symmetry class in turn. Thus, with the usual notation for
this direct product, we write
A ® A 1 1 1 1 1 (= A )
1 2
2
A ® E 2 1 2 0 0 (= E)
2
E s T 6 0 2 0 0 (= T + T )
1
1 2
T ® T 9 0 1 1 1 (= A + E + T + T )
1 2
2 1 2
and so on. These product functions are also representations of the given point
group. The dimension of a product function is the product of the dimensions of the
two functions forming the direct product. Thus the dimension of E (81 T
1
is ne nr, ,
or 6; it is, of course, the character of E (81 T
I
under the E symmetry class. It is self
evident that these direct product representations are reducible (see Section 4.4); the
irreducible representations arc shown above in parentheses. We used the direct
product in Section 3.3.2, and that application might be now reviewed (see also
Appendix Al 1.3).
We can consider here the application of this form of direct product to matrices; it
is quite different from the matrix multiplication considered in Section 2.5.3. For
example, given a 2 x 2 matrix A and a 3 x 3 matrix B, their direct product A (81 B is
formed according to the equation
A ® B
[
a Bi a B]
11: 12
.........................;......................... ~
a B: a B
21: 22
(4.40)
The righthand side is a partitioned form of the fully multiplied product (4.41). We
shall use this result in studying the construction of character tables in the next
section. We note that if the general elements of A and Bare aij and b
k
/, respectively,
then the general element of the direct product matrix, say C, is C(ij)(kl) , but we may
allot it its own (twodimensional) label.
Sec. 4.2] A 1001< at character tables
87
a b a b a b a b a b a b
11 11 11 12 11 13 12 11 12 12 12 13
a b a b a b a b a b a b
11 21 11 22 11 23 12 21 12 22 12 23
a b a b a b b a b a b
11 31 11 32 11 33 12 31 12 32 12 33
A s B =
. (4.41)
a b a b a b a b a b a b
21 11 21 12 21 13 22 11 22 12 22 13
a b a b a b a b a b a b
21 21 21 22 21 23 22 21 22 22 22 23
a b a b a b a b a b a b
21 31 21 32 21 33 22 31 22 32 22 33
4.2 A FIRST LOOK AT CHARACTER TABLES
We will consider Figure 4.1 again, with the reference axes as shown, confining our
attention to the hydrogen atom He. The symmetry operators act on its x, y and z
coordinates in the following way:
E: No change in x, y or z.
C
l
: x ~  x
Y fy
No change in z.
<Y
v
: y ~  y
No change in x or z
<Y
v
' X ~  x
No change in y or z
We could write these results in the following manner:
C
l v
E C
1
<Y
v
<Y
v
'
X 1 1 1 1
Y 1 1 I 1
z 1 I 1 1
xy 1 1 1 1
The effect of the symmetry operations on the product functions x", l, i, xy, zx and
yz can be obtained in like manner. Thus, x", land Z2 transform like z under all
operations of the group, zx transforms like x and yz like y; xy is different, which is
why it is included in the above table. In all, there are four ways in which functions
may transform under C
2v
; we tabulate them with the usual names for the four
representations in the form of a character table:
~ v
E G
<Y
v
<Y
v
2
A 1 1 1 1
2 2 2
Z X , y, Z
1
A 1 1 1 1 R xy
2 Z
B 1 1 1 1 x, R zx
1
Y
B 1 1 1 1 y, R yz
2 X
88
Representations and Character Tables [eh.4
There are no other ways in which new functions can transform: for example, x
3
transforms like x, and x
4
like x
2
. The four transformations AJ, A
2
, B
I
and B
2
are the
labels of the irreducible representations in C
2v
, and the numbers in the body of the
table are the characters ofthe irreducible representations of C
2v
, or just characters.
In the third column of the table, the symbols x, y and z refer to the coordinate axes
(or to translational movements with respect to these axes), and Rs, R
y
and R
z
refer
to rotational movements about the axes indicated by the subscripts. If we are
transforming p orbitals, then because orbitals are named in terms of their axes, it
follows that pz, p, and py transform under C
2v
according to AI, B] and B
2
,
respectively. The final column of the table lists the binary products of the
coordinates.
We speak of x as belonging to, or spanning, the B
I
representation of C
2v
; again, x
is symmetric (+ I) with respect to E and cry and antisymmetric (I) with respect to
C
2
and cry' ; z is totally symmetric under all operations of C
2v
. If we form another
function such as x
3
+/ + z, it is clear that it does not belong to any of the reducible
representations in C
2v
. However, x
3
transforms like x and l transforms like z. Thus,
the given function spans the irreducible representations 24
1
and B
I
•
From the B
I
representation of C
2v
cry'
I
E
I
f        =   _ " : " '   _  
we may form a table by replacing each operator in a group multiplication table (see
Section 3.2.3) with +1 orI:
1 1 1 1
1 1 1 1 1
1 1 1 1 1
1 1 1 1 1
1 1 1 1 1
Each of the products of +I or I with +I or I under multiplication is correct, so
that B
I
is true representation in C
l v
; this same situation arises for any of the
irreducible representations. The point group C
2v
is Abelian: in all Abelian point
groups the characters are all +I or I (see also Section 4.2.2).
We note a certain dependence of the spanning upon the choice of axes. On the
one hand, if for point group C
2v
, for example, cry is chosen as the zx plane and cry'
as yz, then the character table given above is obtained. On the other hand, if we
interchanged the x and y axes. x would span B
2
, y would span B
1
, and so on. The
character of B) under cry remains as +I (see Section 4.2.2), so that to retain right
handed axes the direction of z would have to be reversed.
Sec. 4.2]
A look at character tables
89
4.2.1 Orthonormality
If we consider any irreducible representation, such as B
I
in Czv, form the sum of the
products of the characters under the symmetry operators, each with itself, and then
normalize the result by dividing by the order h of the group, we obtain
±{(I x I) + [(I) x (I)] + (l x I) + [(I) x (I)]} = I
whereas if we carry out the same process, but taking the product of each character
with that, say, for the B
2
representation, we find
.!. {(l x I) + [(I) x (I)] + [1 x (I)] + [(I) x I)} = 0
4
Similar results would be obtained with other pairs of irreducible representations,
and these equations are examples of orthonorma/ity relationships. In general, each
individual term would be multiplied by the symmetry class number in forming the
sum, but they are all unity in Czv. We note en passant that the number of symmetry
operators in a group and its order are numerically one and the same.
The term 'orthonormal' combines the terms 'orthogonal' and 'normal'. Two
coordinate axes or two functions are orthogonal when there is no component of one
on the other. Thus, mutually perpendicular x, y and z axes are orthogonal: anyone
of them behaves independently of the other two. Normalized functions have equal
weight, usually unity; in the above examples lIh acts as a normalization constant.
EXAMPLE 4.3. We determine whether or no the functionsji andJi are orthonormal over the
range ±1t:
f = cos(V)
1
f
2
sin(V)
o.
~ r r .
1
Furthermore,
+ cos(2V)]/2 dV
rr
sin(V) dV = I sin(2V)/2 dV
rr
rr
= N: I [1
rr
and simi larly f .
2
rr
N: I cos
2(V)
dV
rr
= l/v'rr,
For normality, N
1
rr
N N I cos(V)
1 2
rr
Thus.ji andJi are orthogonal, and become orthonormal if each is multiplied by 1hl1t.
4.2.2 Notation for irreducible representations
The symbols AI, A
2
, B] and B
2
are part of the Mulliken notation[12
j
for one
dimensional irreducible representations. For twodimensional (doublydegenerate)
representations the symbol used is E, and threedimensional representations, which
we shall encounter in Td and Oh, are indicated by T. Multidimensional irreducible
representations arise when two or more directions or functions are related by
symmetry. Thus, in C
4v
, for example, the x and y directions are related under the C
4
symmetry operation, and in the character table for that point group they appear,
coupled, against the doublydegenerate E irreducible representation.
90
Representations and Character Tables [Ch.4
e = exp (i 2rr/3 )
The symbol A is used for an irreducible representation that is symmetric
(characters, +1) with respect to the C, or S, operation of highest degree; if the
irreducible representation is antisymmetric (1) under the same rule, it is labelled
B. In the groups C
1
, C, and C, where the operations C, (n > 1) do not appear, all
irreducible representations have the primary label as A.
A centrosymmetric group G
i
may be regarded as the direct product of the groups
G and C, , or G and the operation i. For a given type of irreducible representation A,
B, ..., the characters of those symmetry operations that are not in both 6.; and 6. are
of opposite sign in the irreducible representation of subscript 'u' and of the same
sign where the subscript is "g' (Gel. ungerade = odd, gerade = even); the signs of
the characters in G that arc common to both G and Gj are determined by the signs
in 6.. Thus, in 0
3
and Old the 'A
2
' type irreducible representations have the
following form.
E 2C 3C'
i
2S
3<rd
3 2 2
6.: en A 1 1 1
3 2
{
A 1 1 1 1 1 1
i G: en
2g
3d A 1 1 1 1 1 1
2u
If a point group contains the operator (Jh but no i, the irreducible representation
labels are singly primed if the character is +1 under (Jh and doubly primed
otherwise, as in C, and 0
311
, for example.
For A and B representations. the subscripts 1 and 2 show, respectively, a
symmetric (l) or antisynunetric (1) character with respect to a C
2
axis
perpendicular to the principal en axis or, in the absence of this symmetry, to a c,
plane. For multidimensional representations. the subscripts 1, 2, ... are added to
distinguish between nonequivalent irreducible representations that are not
separated under the above rules.
Complex characters
In a small number of point groups complex characters arise. In C
3
, for example,
which is Abelian, the complex characters E and E* exist, where E = exp(i2n/3);
exp(i2n/3) may be regarded as an operator that rotates a vector by 2n/3, or 120°,
anticlockwise in the complex plane (of an Argand diagram). For this particular
value of c, s + c* = 1 and, for all values of E, c*c = cc* = 1. The two irreducible
representations involving complex characters are normally bracketed under the
(twodimensional) label E. as in C
3
:
E C C
2
3 3
A 1 1 1 z : R
2 2 2
, Z
x + y ; z
•
2 2
E {
1 e e
}
(x, y); (x  y , xy)
•
(zx, yz) 1 e e (R , R )
x y
Sec. 4.3] The orthogonality theorem
91
Point groups with complex characters are not often encountered in molecules. We
shall, however, make use of some of them in studying symmetryadapted linear
combinations of atomic orbitals in a later chapter.
Linear groups
Linear molecules belong to point group C",v (HF. COS) or D"'h (H
2
, CO
2
) and we
will consider the character table for Coov:
c.,
E
2Cq,
exr
00 V
r+ (A )
1 1 1
222
Z X +y +z
1
r
(A
2
) 1 1 1 R
z
IT (E ) 2 2 cos(q,) 0 (x ,y); (R , R ) (zx, yz)
1 X
Y
2 2
!J. (E ) 2 2 cos(2q,) 0 (x y , xy)
2
4>
(E ) 2 2 cos(3q,) 0
3
The symbol C t indicates a rotation by an angle <p of any value, including
infinitesimal. An infinite number of such rotations is possible, together with an
infinite number of vertical symmetry planes. We can form D
Xl h
by the direct product
of C
oov
and I, However. we should note that the signs of the characters for the pairs
of irreducible representations n
g
, Il., ... and ... do not follow the rules given
above for other groupsl"'. In the linear groups, the Greek symbols are often used in
place of the Mulliken notation. Additionally, the use of primes on the symbols for
irreducible representations is changed here to + and  signs, determined by the sign
of the character under the o, operation (see also Appendix II).
4.3 THE GREAT ORTHOGONALITY THEOREM
Now that we have spent some time studying and manipulating representations and
character tables, we consider a basic result concerning the terms of those matrices
that relate to the irreducible representations of point groups. This proposition is
known as the great orthogonality theorem: for any two irreducible representations
ra. and r the terms of the related matrices Det(R) and satisfy the equation'!"
17)
LD· (R) .. Da(R) =
R a 1) 'J pq
(4.42)
where D: (R)(i refers to the complex conjugate of Da.(R)(i, and the sum extends
over all symmetry operations R: each 8 is a Kronecker delta. When all characters
are real the term Det(R)!! may be used in a place of its conjugate. In applying this
theorem. we would assemble the D
et
 and and select particular values
92
Representations and Character Tables [eh.4
for i.] and p, q. For the ijth term in D
u
and the pqth term in Dp , we form the sum
of the products D: (R)u D1l(R)pq over all symmetry operations R in the group and
compare the result with the value of the righthand side of (4.42); n« and np are the
dimensions of the two irreducible representations fa. and I'p, respectively. However,
before applying this theorem to particular examples it is pertinent to consider first a
number of important results that follow directly from it.
(a)
The characters of the two representations are orthogonal so that 8a.p = 0; then we
have
r D· (R) .. Da(R) = O.
L (X 1) IJ pq
(b) fa. = f p: ex = (8
Ull
= I):
If i ;t: P orland) ;t: q, Ojp orland O,q = 0: then
[ D· (R) .. Da(R) = O.
R (X 1) IJ pq
(c) fa. = f p (8
up
= I); i = P and) = q (o;p = O,q = I):
Then
(4.43)
(4.44)
r ID (R). .1
2
=
L (X 1)
h
n
(X
(4.45)
(d) We refer to the matrices in (4.14) that were developed to form one
representation of point group C
3v
; there are six of them because the order h for this
group is six. Equation (4.45) implies that the set of ijth matrix terms in an
irreducible representation may be looked upon as a vector in hdimensional space,
and there are h
2
such vectors: thus. for C,v there is a total of 36 ij matrix terms (see
Example 4.4). Do not worry about visualizing hdimensional space: it may be
regarded as a mathematical device for collating h related quantities in a vectorlike
manner.
The vectors arc mutually orthogonal (see Section 4.2.1), and the square of the
length of any vector is hll1«, from (4.45). Because there can be no more than h such
orthogonal vectors, it follows that
r
r n:
L ... :S h,
<x=1
(4.46)
where r refers to the total number of irreducible representations. A more detailed
analysis'!" shows that L:,«11 is exactly equal to h.
i=)andp=q:
Sec. 4.3]
The orthogonality theorem
93
We are using here the diagonal terms of the Dmatrices; then
\' D· (R) . .D
Q
(R)
L
R
a 11,.. pp
=
(0.
Ip
(4.47)
Consider the sums over all i and p:
na {n •
\' \' D (R) . . DQ(R)
L L a 11 I" PP
• R
1=1 p=l
=
)0..
L IP
p=l
(4.48)
The lefthand side sums, over i and p, may be written as
n
a •
\' D (R) ..
L a 11
i=l
=
(4.49)
since X is the trace of a Dmatrix. Summing now over all operations R, we may
write
k
Lgi
•
=
X (R).
a 1
i=l
(4.50)
where k is the number of symmetry classes and gi is the number of operations in the
ith such class. On the righthand side of (4.48), the double summation will be
nonzero only for p =i (and n« = n ~ ) , when it becomes
n
a
L1 = n
a·
(4.51)
i=l
Then, by combining results from (4.48)(4.51), we obtain
k
\' g.X (R) .XQ(R) .
L 1 a 1,.. 1
i=l
=
(4.52)
the nonzero result, for ex = ~ , is
k
\' g.1 X (R) .1
2
= h.
L 1 a 1
i=l
(4.53)
Finally, we consider the number of irreducible representations to be expected for
any group. Consider the set of numbers .Ji zaCR); as i ranges over k symmetry
94
Representations and Character Tables [Ch.4
classes for a given value of a. The set forms a kdimensional vector with
components Va..I = Ji Za(R),. If the group has r irreducible representations there
are r such vectors which, from (4.52), are orthogonal: L va/ = Va/ = h5a./3.
There can beno more than k orthogonal vectors in kdimensional space (consider i,
j and k of threedimensional space), so that
r s k . (4.54)
If we accept the equality of (4.46), it follows that r is exactly equal to k, that is, the
number of nonequivalent irreducible representations in a point group is equal to the
number of symmetry classes.
We shall now consider some examples to show the use and value of the
relationships that we have just developed. We use the point group C
3v
, with which
we have now a certain familiarity.
EXAMPLE 4.4. We examine the application of (4.42) in point group C'v. Its character table
is given below in an expanded form rather than grouped into classes. Compare this table
with that in Example 4.5, and note that it shows clearly how each entry in the normal table
is the trace Xof a Dmatrix. We recall that C, and C are in one class, and (lv, (Iv' and (Iv"
form another class; E is always in a class by itself. The irreducible representations f
l
, f
2
and f, are normally listed as AI, ,12 and E: all characters here are real.
E C C
2
cry
..
C
3v
3 3
cry cry
r (1) (1) (1) (1) (1) (1)
1
r (1) (1) (1) (1) (1) (1)
2
V:
J
!:J
r
[
1 0
J
[
1 0
J
3
0 1 o 1
We know that if any of Dip or b
JlJ
is zero, then the righthand side of (4.42) is zero.
Hence, we consider the following two cases:
(1) a =13 = I; 11" = I; i =P =2;j =q = I
Thus, (4.42) reduces to (4.45) and we have
LRID
1
(R )21 1
2
= 1
2
+ J2 + ]2 + ]2 + 1
2
+ ]2 = () (= hind
This equation exempli ties a vector in IIdimensional space. Similar results are obtained for
the other Ij terms, and for (1 =(3 =2.
(2) a=13=3;n,,=2;i=p= l;j=q=2
Sec. 4.4] How to reduce 1I reducible representation
95
EXAMPLE4.5. The more usual (partial) character table for C3v is:
C
3v
E 2C
30'y
3
A 1 1 1
1
A 1 1 1
2
E 2 1 0
From the exact formof (4.46), we have tor the three representations
222
n
A
+ n
A
+ n
E
6.
1 2
For h = 6, the integer values tor II must be I, I and 2, corresponding to the dimensionality of
AI, A2 and E, respectively. This equation is obeyed by each column of the character table,
taking into account the number of operations in each symmetryclass.
EXAMPLE 4.6 Equations (4.50) and (4.53) refer directly to characters, the first of them
being the more general. Using the irreducible representations AI and A2 of C3v, the right
hand side 01'(4.50) sums to
(1 x I x 1) + (2 x I x I) + [3 x I x (I)] = 0
whereas for A2and A
2,
we obtain
(I x 1 x I) + (2 x I x I) + [3 x (1) x (I )] = 6
which is the value of the order It ofthe group. TIle same result follows from (4.53), because
all characters in C3v are real.
EXAMPLE 4.7. We can use (4.53) also to obtain the characters of a representation given
those of the others, because they are not all independent. Given the characters of AI and A2,
we obtain
XE(E) + 2XE(C
3
) + 3XE(O'y) = 0
XE(E) + 2XE(C
3
)  3XE(O'y) = 0
Subtracting gives 'Y,.E(O'v) = O. and adding gives XE(E) = 2XE(C
3
) . From (4.53), it
follows that XE (C
3
) = ±I. Since XE(E) = 2 (a twodimensional representation), we
must choose XE(C
3
) =1.
4.4 HOW TO REDUCE A REDUCIBLE REPRESENTATION
A matrix representation r that is reducible to a set of irreducible representations
can be blockfactored. as exemplified by (2.65), Section 2.5.5. The set of blocked
matrices, or subtnatrices, D; (R) comprises the irreducible representations of r. A
given type of irreducible representation may appear among the blocked submatrices
once, more than once or not at all.
We consider a set of Dmatrices D(W), D(X), D(Y) and D(Z) that exist in a
blockfactored matrix which. therefore, forms a reducible representation for a given
point group. and among which we assume
D(X)D(Y) = D(Z). (4.55)
96 Representations and Character Tables [Ch.4
We will replace these matrices by another set D(W'), D(X'), D(Y') and D(Z') that
are irreducible representations of the same group. We define a matrix Q such that
Q1
D(W)Q
Q1
D(X)Q
=
=
D(W' )
D(X' )
}.
(4.56)
and so on. From (4.55), (4.56) and (2.7),
D(X' )D(Y') = =
= = D(Z' i. (4.57)
Thus, the two sets of matrices. related by similarity transformations, are isomorphic
and their characters are equal (see also Section 2.5.3).
Consider the 9 x 9 reducible matrix (4.26); its trace Xr<d is 3. It is evident also
that Xred is the sum of the traces of its irreducible submatrices:
Xred = XI + X2 + X3; (4.58)
since the submatrices are equal, we have
(4.59)
Generally, if Xred (R) is the character of a reducible matrix r under the operation R,
we have
x (R)
red
=
r
'\ a X (R).
L a a
a=l
(4.60)
where r is the number of irreducible representations (the same as the number of
symmetry classes), X",(R) is the character of the «th irreducible representation for
the operation Rand G" is the number of times that it appears in the reducible
representation under the operation R. From (4.50) and (4.52), assuming for
simplicity that all characters are real [if not, we use X: (R»), we know that
L = (4.61)
R
For each operation R, each side of (4.61) is multiplied by G
a
and summed over ex.:
LXQ(R) '\ a X (R)
R fJ La a a
=
(4.62)
Substituting from (4.60), and since L", = hIa we obtain, because Ia
G",0"'13 is nonzero only for Ix' =
'\ XQ(R)X (R) = a h.
L 1' red a
R
(4.63)
Sec. 4.5] Constructing a character table
97
whence it follows that the number of times that the a.th irreducible representation
appears in the given reducible representation r is
k
a = hI \ X (R) X (R) = I \ g . X ( R). X (R) .; ( 4 . 64)
IX L. IX red h L. 1 IX 1 red 1
i=l
gi is, as before, the number of operations in the ith symmetry class, 'X,<t(R)i is the
character of the ith symmetry class for the oth irreducible representation and the
sum is over all k classes.
EXAMPLE 4.8. Let a representation in point group C3v be given as
r
E
3 a
1,
Reference to the characte table (given under Example 4.3, or in Appendix 11) shows that
this representation is reducible. By inspection, we could write I' = Al + E. Confirming
through (4.64):
1
 [(1 x 1 x 3) + (2 x 1 x 0) + (3 x 1 x 1)1
6
1
[(1 x 1 x 3) + (2 x 1 x 0) + (3 X (1} x 1)1
6
0,
1
"e 6[(1 x 2 x 3) + (2 x {1} x 0) + (3 x 0 x 1)1 1
which leads to I'> Al + E
EXAMPLE 4.9. If, however, we are working in point group C3, a representation may be
given by the first three Dmatrices of(4.14):
~ I
E
3 o o
2,
The character table for C3 has been given in Section 4.2.2. By inspection, or by applying
(4.64):
aA = 1
ar = 1
ar = I
which means [red =A + I' + [*. However, if we were to operate by first combining I' and [*
to formE, giving 2 1 1 for this irreducible representation, then
~ [(1 X 2 x 3) + 0 + 01
3
leading to [red = A + 2£, which is incorrect.
4.5 CONSTRUCTING A CHARACTER TABLE
We introduced character tables in Section 4.2, and subsequently developed a
number of relationships involving representations and their characters. In this
98 Representations and character tables
[Ch.4
section we summarize those findings that will enable us to construct and validate a
character table.
1) The squares of the (integral) dimensions of the irreducible representations ofa
point group summed over the number r of irreducible representations is equal to
the order h of the group:
r
L ~ = h.
Q'.=1
(4.65)
2) The number r of irreducible representations of a point group is equal to the
number of symmetry classes in the group:
r = k. (4.66)
3) The first row of characters (an A, A', A
g
, AI, A; or A1g) irreducible
representation) in the character table of a point group are each +1.
4) The squares of the characters of the identity matrix of a point group summed
over the irreducible representations is equal to the order of the group:
r
(4.67)
(4.69)
Q'.=1
5) The rows of the character table of a point group, summed over the number of
symmetry classes, obey the equation:
k
Lgi
X;(R)i X(3(R)i
= hOQ'.(3' (4.68)
i=l
6) The columns of the character table of a point group, summed over the number
of irreducible representations, obey the equation:
r
\' X· (R).;¥ (R). = hO
I
' ) "
L Q'. 1 'Q'.) 
Q'.=1 gi
7) The dimension nred of a reducible representation is equal to the sum of the
dimensions n« of the several irreducible representations into which it may be
decomposed:
r
n
red
=
Q'.=1
(4.70)
Let us assume now that we wish to construct the character table for the point group
2 ' ,
D3{E, C
3
, C 3 , C 2 , C 2" C ~ ..} (see note 10 to Table 3.5); h = 6. Grouping the
operations into classes, we have, by inspection:
Sec. 4.5] Constructing a character table
99
2C,
From (4.66) we know that the number of irreducible representations is 3. From
(4.67) we know that we need three integers, the sum of the squares of which is 6;
the only possible values are I, I and 2. Using the fact that the first row consists of
unit characters, we can assemble the following character table:
D
3
E 2C 3C
'
3 2
r 1 1 1
1
r 1 a b
2
r 2 c d
3
From (4.68) we have
1 + 2a
2
+ 3b
2
= 6
}.
(4.71)
1 + 2a + 3b = a
(4.72)
}.
a = + 3d 2 + 2c
whence a = I and b = I. Using (4.68) again we obtain
4 + 2c
2
+ 3d
2
= 6
whence c = I and d = 0, thus completing the character table. We consider now a
final, more difficult example.
EXAMPLE 4.10. We construct the character table for D
311,
which may be written D311 {E, C3,
2 " O' "
C 3 , C 2 ' C 2' , C ~ .., ah, 83, 8
3
, O'v' O'v' O'v }. The group is of order 12, and the symmetry
classes are E, 2C3, 3C ~ , all, 28
3
, 3a
v
. Thus, k = () and, from (4.66) r = 6.
From (4.65), the only satisfactory set of integers nO. is I, 1, 1, 1, 2 and 2. Thus, we can
write a reasonable character table as shown below (see Section 4.2.2); the structure of the
table is indicated by the dottedline partitioning.
D
3h
E 2C 3C
' ab
25
3a
v
3 2 3
A' 1 1 1 1 1 1
1
A' 1 a b 1 a b
2
E
'
2 c d 2 c d
A I I
1 1 1
1 1 1
1
A I I
1 a b
1 a b
2
EI I
1 c d
2 c d
100
Representations and Character Tables [eh.4
From the halfE' row, using (4.68) with ex =~ =E', we have 4 + 2c
2
+ 3d
2
=6, or 2c
2
+ 3d
2
=2. The only logical answer to this equation is c =±1, d =0. Applying (4.68) to the halfE'
and halfA' rows together, 2 + 2c =0, whence c =1.
Using (4.69) with the E and 3C ~ columns, 3 + 3b + 3 + 3b = 0, whence b = I.
Finally, applying (4.68) to the halfA; and halfA ~ rows together, 1 + 2a  3 = 0, whence
a =1.
We can now complete the character table:
D
3d
E 2C 3C' 25
30"v 3 2
O"h
3
A' 1 1 1 1 1 1
1
A' 1 1 1 1 1 1
2
£' 2 1 a 2 1 a
A' ,
1 1 1 1 1 1
1
A' ,
1 1 1 1 1 1
2
E.' ,
2 1 a 2 1 a
We can construct character tables also by making use of the direct product
relationships discussed in Section 4. I.5. Consider first the direct product c., 0 C, .
Setting down the character tables we have
A
B
E
(1)
(1)
(1)
(I)
C, E
(1)
(1)
i
(1)
(I)
We can see from the following scheme the symmetry operations that we should
expect to arise from the direct product of C
2
and C, :
C
2
,
E
E/
/
C
2
Each character in these tables is actually a I x I matrix, as shown, and the direct
product may be formed by taking each term of C
2
in turn and multiplying the four
terms of C, by it, thus:
C
2h
E C
i
O"h
2
A 1 1 1 1
9
B 1 1 1 1
9
A 1 1 1 1
u
B 1 1 1 1
u
Sec. 4.5] Constructing a character table 101
The first and third lines are clearly A representations because the character is +1
under C
2
; they are labelled A
g
and Au, respectively, because of their behaviour
under i. In a similar manner, we attach the labels B
g
and Bu.
For a further example, we consider the direct product Cj ® C
3v
. As before, we set
out the character tables and form the direct product. However, the degenerate
representation E in C
3v
is not itself a matrix, but the trace of a 2 x 2 matrix. Thus,
we need to write E fully, and this entails expanding the symmetry classes, as we did
in Example 4.4. Thus, we have
Cj E C
2
A
(1) (1)
g
A (1) ( 1)
u
E C C
2
.
cry
..
C
3v
3 3
cry cry
A
(1) (1) (1)
(1) (1) (1)
1
A
(1) (1) (1) (1) ( 1) (1)
2
~ ~ l [  ~ V ~ l [1 0) [ ~ V ~ l [  ~ ~ ~ l
[:
0J[l
E
1 vi
1 y3 _1 a 1 v ~ ! t ~ !
2 2 2 2 2 2 2
Again, we can develop the symmetry operations to be expected from the products.
For example, iC
3
=S {;; this relationship, and others, are illustrated by the
stereogram in Figure 4.4.
The product of C
i
and C
3v
contains twelve columns and six rows, shown below in
two parts corresponding to the two columns of Cj . To make the complete table, the
two parts should now be considered as joined along the vertical dotted line; the
Fig. 4.4 Stereogram to show the operations C3, i and S ~ . The equivalence iC3 =S ~ is
shown by the scheme; note that iC ~ = S6:
102 Representations and character tables [eh.4
joined along the vertical dotted line; the irreducible representations have been given
the 'g' or 'u' subscript according as the characters of the matrices under i are +1 or
1, respectively.
Next, we collect the operations into classes and form the traces of each matrix,
which leads to the conventional character table for point group D
3d
.
D
3d
E C C
2
•
3 3 cry cry
A (1)
19
A (1)
2g
(1)
(1)
(1)
(1)
(1)
1)
(1)
(1)
(1)
(1)
E [1 0] [1 0]
g 0 1 1. 1. 0 1 1. 1.
2 2 2 2 2 2 2 2
A
lu (1)
A
2u (1 )
(1)
(1)
(1)
(1)
(1)
1)
(1)
(1)
(1)
(1)
E [1 0] [1 0]
u 0 1 _1. _1. 0 1 1. 1.
2 2 2 2 2 2 2 2
S
6
C'
2
(1) (1) (1) (1) (1) (1)
(1) (1) (1) 1) (1) (1)
[
1 0] [1 0]
o 1 1. t:? 1. 0 1 V:? .!. .!.
2 2 2 2 2 2 2 2
1) (1) (1) 1) (1) (1)
1) (1) (1) (1) (1) (1)
[
1 0] [1 0]
o 1 1. 1. 0 1 _1. 1.
2 2 2 2 2 2 2 2
Sec. 4.5] Constructing a character table 103
D
3d
E 2C 3C
i
25
30"d 3 2 6
A 1 1 1 1 1 1
19
A 1 1 1 1 1 1
2g
E 2 1 0 2 1 0
g
A 1 1 1 1 1 1
lu
A 1 1 1 1 1 1
2u
E 2 1 0 2 1 0
u
The above procedure may be illustrated in the manner used for ~ h . We find the
symmetry operations introduced by i combining with the symmetry operations of
C
3v
, and then arrange them in their symmetry classes:
C;
E
i
2C
3
2C
3
3C'
2
The apparent anomaly 30"~ E30"d is simply a change of notation because the
symmetry planes in D
3d
lie between twofold axes (see Section 3.3.2, Notes to Table
3.5) and are thus designated ad. We can now form the direct products in terms of
the irreducible representations, using the character tables for the two groups. The
character table for D
3d
is obtained, identical to that derived above, and the
partitioning shows its relationship with C, and C
3v
.
E
ae,
Cj
E
A ® A
1 g
A
2
® A
g
E ® A
g
1
1
2
=
=
=
A
19
A
2g
E
g
1
1
1
E
1
1
2
1
1
o
2C
3
1
1
1
3C
2
1
1
o
A
g
A
u
i
1
1
2
1
1
25
6
1
1
1
1
1
30"v
1
1
o
® A
u
® A
u
A ® A
1 u
A
2
E
=
=
=
A
lu
A
2u
E
u
1
1
2
1
1
1
1
1
o
1
1
2
1
1
1
1
1
o
104
Representations and Character Tables [Ch.4
These procedures can become a shade laborious with larger character tables.
However, while we shall not be greatly concerned with the construction of character
tables, it is important to understand the ways in which one character table may be
related to another, and how the characters in a given table are related one to the
other. All the character tables for the point groups that we have considered, or will
need to consider, are given in Appendix II. Further information is available[18] for
readers who wish to explore character tables in more detail. It is important to note,
however, that not all authors write the symmetry classes in the same order,
particularly with the high symmetry groups like D
4h
and Oh. Care should be taken to
ensure consistency in working with character tables.
4.6 HOW WE HAVE USED THE DIRECT PRODUCT
At this point we recall the uses that we have made of the concept of the direct
product. In Section 3.3.2, we met it as a way of deriving certain point groups from
others, thus:
c, ® C
1
= D
Zh
,
in which we determined all products of the symmetry operators of the groups C
zv
and C,.
Then, in Section 4.1.5, we derived representations of point groups for product
functions, subsequently reducing them, by the direct product of two or more
irreducible representations. Thus, if in C,v the wavefunctions 'V" 'Vz and q/, span
A
z
, E and E, respectively, the product \I'1'V2'V3 spans a representation given by the
direct product
A
z
® E ® E
We may evaluate this product from the character table for C
3v
:
E 2C 30
3 v
A 1 1 1
2
E 2 1 a
A ® E ® E 4 1 a
2
that is,
A
2
® E ® E = Al + /1z + E.
Here, we are multiplying just the characters of the matrices.
If we set the multiplication of the matrices in full, say for the symmetry class C
3
of C3v" we obtain
Problems 105
1 ';3 ';3 3
4 4 4 4
(1) @ [
1 ';3
] [
1 ';3
]
';3 1 3 ';3
2 2 2 2
(1) e
4 4 4 4
';3
®
';3
=
';3 ';3 1 1 3 1
2 2 2 2 4 4 4 4
3 ';3 ';3 1
4 4 4 4
1 ';3 ';3 3
4 4 4 4
';3 1 3 ';3
=
4
4 4 4
';3 3 1 ';3
4 4 4 4
3 ';3 ';3 1
4
4
4
4
and the trace of this resultant matrix is I, as we found above.
Finally, in Section 4.5, we used the direct product in deriving a character table.
There, effectively, we formed the products of both the symmetry operators and the
characters; with the labels for the irreducible representations being adjusted
accordingly:
~ h
E C
CTh
2
Cj
E
i
C
s
E CT A 1 1 1 1
g
A 1 1 A' 1 1 B 1 1 1 1
g ® = g
A 1 1
AI I
1 1
A 1 1 1 1
u
u
B 1 1 1 1
u
PROBLEMS 4
4.1 Construct the Dwatrices for the operations C
6
(z) and C ~ (y). Determine the
nature and orientations of the operators formed by the products
(a) D(C
6)D(C2
' ) and (b) D(C
2')D(C
6
) .
4.2 The Dmatrix below may be formed in two ways. What are they?
[
1/2 ';3/2
D(C
2
) = ';3/2 1/2
3
0 0
~ ]
4.3 Use the 9 x 9 Dmatrices in Section 4.1.3 to obtain a representation for the
water molecule and reduce it.
106
Representations and character tables [Ch.4
4.4 How might the irreducible representations found in the previous problems be
divided among the possible molecular movements or displacements?
4.5 Given the following representations, find the irreducible representations in
each case.
(a) ~ v : 3 I 3 I
(b) C
3v:
5 2 I
(c) C
3h:
3 0 I 3 0
(d) C
4v:
5 I I 3 I
(e) D
6h
: 6 0 0 0 o 2 0 0 0 6 2 0
(1) 0h: 9 0 I I 3 3 0 3 I I
4.6 ButaI,3diene belongs to point group C
2h
. Determine the Dmatrices for its
symmetry operations. Deduce the character table for this point group.
4.7 Write down a I', representation for butaI,3diene ( ~ h ) based on the carbon pz
orbitals, and then reduce it.
4.8 Show that the irreducible representations in point group C
3
are orthonormal.
4.9 Complete the partial character table given below for D
3h
:
D
3h
E 2G 3G'
crh
25
3cr
v
3 2 3
A 1 1 1 1 1 1
19
A 1 1 1 1 1 1
2g
E
g
A
lu
A
2u
E
u
4.10 Consider the molecule of sulfur dioxide S02, point group C
2v.
Set up a
representation using the two SH bond vectors rl and r2 and the HSH bond
angle a; reduce the representation, if necessary. What important structural
feature is present in the Dmatrices for the symmetry operations of this point
group?
4.11 Form the direct product representation E
1
0 T
1
0 T
2
in point group T
d
and
find the irreducible representations of which it is composed.
4.12 Using the appropriate character tables, evaluate and identify the direct
products (a) c. 0 C
3,
and (b) D
2
0 c,
4.13 Determine r 3n for the following species; then, reduce each representation
obtained.
(a) Brf', (C
4v):
Set x through the Br atom and two F atoms in the plane of the
four F atoms; cry is the xz plane.
Problems 107
(b) [N0
3
r (D
3h
): Set x through the Nand 0 atoms and CJ
v
as the xz plane.
(c) [PtCld
2
 (D
4h):
Set C
2
' through along PtCl bonds, with CJ
v
the plane of
C
2
' and z
(d) Ni(CO)4 (T
d
) : It is helpful to place a tetrahedral molecule inside a cube such
that the NiCrO bonds lie along the body diagonals of the cube (see Example
6.1 later).
4.14 Determine the irreducible components of the representation given by the out
ofplane p orbitals of the B atom in a planar molecule of formula AB
3
.
4.15 Show that equation (4.47) for a. = ~ may be written as
Lx·CRl
i
XCRl j = hOipl
n
where n is the dimension of the irreducible representation ex (or ~ ) . What is
the result of applying this equation in the following cases: (a) C
6v
, j =p =B
2
,
(b) C
4h
, i =P =E
g
, and (c) D
3h
, i = E", j == A 2 ?
5
Group theory and wavefunctions
No annihilation without representation.
Arnold Toynbee (18891975): on U'N,«). 1947
5.1 INTRODUCTION: USING THE SCHRODINGER EQUATION
In this chapter we consider briefly the Schrodinger equation and begin to apply
group theory to chemical systems. We know that an exact solution for the
Schrodinger equation is possible only for oneelectron chemical species, such as the
hydrogen atom[l9
1
or the hydrogenmolecule ion, H;. For other species
approximations are employed, and we need to lay groundwork whereby
simplifications may be brought about through the symmetry of a species under
consideration.
We shall be concerned with the limeindependent Schrodinger equation, because
the systems that we shall consider will not be evolving with time. This
fundamental, quantummechanical equation in its most concise form may be
written as
H'I' = Ell, (5.1)
where H is the Hamiltonian (linear) operator, which depends upon the numbers of
electrons and nuclei and their masses, \.p is the total wavefunction, which depends
upon the coordinates of the electrons and nuclei; E is the total energy of the system
and is a constant. Comparison with (2.44) shows that (5.1) is an eigenvalue
equation, where tj/ is the eigenfunction and E the eigenvalue.
We introduce here the BornOppenheimer approximation, which divides (5.1)
into two parts. It assumes that the mass of a nucleus is sufficiently greater (ca 1835
times) than that of an electron for the nucleus to be treated as effectively stationary,
with the electrons moving in its field. Thus, we obtain the subdivisions
Htt' = E.tt',
Hcp = Ec ,
where the terms have meanings as follows
(5.2)
(5.3)
The Hamiltonian operator for the electron H is given by
h
2
H = __\7
2
+ Y. (5.4)
2 ~ l
The first term on the righthand side is the electronic kineticenergy operator,
where h ("crossh') = hl(2rr), h being the Planck constant, 11 is the reduced mass of
an electron and a nucleus, given by[20) 1111 =(lime + limn), and \72 is the Laplacian
operator (see Appendix 5); Y is the potentialenergy operator, which depends upon
Sec. 5.2] Wavefunctions and the Hamiltonian Operator 109
the interactions between electrons themselves and between electrons and nuclei.
The wavefunction 'P is governed by the coordinates of the electrons, and E is the
electronic energy.
The Hamiltonian H refers to the nucleus, and is given by
H =
_ ~ n 2 V
v + ,
2m
n
(5.5)
where m« is the mass of the nucleus. The terms on the righthand side are,
respectively, the kineticenergy and potentialenergy operators for the nucleus; the
latter, V, depends upon both £. and internuclear repulsions. Evidently, £. is required
before a solution of (5.5) could be attempted. The wavefunction q> depends upon the
coordinates of the nuclei alone. There are situations, such as highly excited
rotational states, where the BornOppenheimer appproximation breaks down, but
our applications will not require consideration of this effect.
5.2 WAVEFUNCTIONS AND THE HAMILTONIAN OPERATOR
The Hamiltonian operator H for a system of electrons and nuclei governs its total
energy E, from (5.1). The energy is constant and must, therefore, remain invariant
under the action of any symmetry operation R. It follows that the Hamiltonian also
is unchanged by the action of R, so that OR and H commute, where OR is the
operator that corresponds to the symmetry operation R:
HO
R
= ORH . (5.6)
A similar argument applies to the electronic and nuclear Hamiltonian operators
individually. It is easy to see from (2.2) that H commutes also with a scalar
constant. These relationships may be proved fully!I?), but that will not be our
concern here. We can see, less rigorously, that because the potentialenergy
operator V is a function of the relative positions of the electrons and nuclei, it is
unchanged by symmetry operations, which apply to the species as a whole: if r and
r' refer to the configurations of a system before and after a symmetry operation R,
respectively, then
(5.7)
The same argument may be applied to the nuclear term Vand, since both £. and E
are constants, it follows that the kineticenergy operators also are invariant under
symmetry operations. We may point out here that it is not uncommon for the
symbol for a symmetry operation to be used in an equation like (5.6) or (5.7) in
place of the operator symbol: as long as the meaning is understood, no harm is
done (see also Section 5.3.1).
We have alluded to degeneracy in Section 4.2.2, when discussing the notation for
irreducible representations. If there are two functions 'PI and 'P
2
that are solutions
of (5.1) and which lead to one and the same eigenvalue for the energy, the
eigenvalue is degenerate, doublydegenerate in this example. This case may be
extended to the important linear combination theorem.
For any particular eigenfunction 'P we have
H'P = E'¥ (5.8)
110 Group Theory and Wavcfunctions [Ch.5
where E is the eigenenergy of tp. Now consider the wavefunction <D to be
compounded from a basis set of functions tp 1, tp2, ... tpn in the relative proportions
Cl, C2, ... c; that is,
IIi =c IIi + c IIi + ... + c IIi =, c .1Ii ..
1 1 2 2 n n L. 1 1
1
For the linear combination (5.9),
HIIi = EHc.lIi. = , c.HIIi. = , c.EIIi. = E' c.lIi.
. 1 1 L. 1 1 L. 1 1 L. 1 1
1 1 1 1
so that E is also an eigenvalue for the combination \jl, (5.9).
(5.9)
EIIi, (5.10)
5.2.1 Properties of wavefunctions
We shall be concerned, normally, with electronic wavefunctions and, therefore,
with the Schrodinger equation as expressed by (5.2). Any acceptable wavefunction
\If for an electron must possess certain important properties. The interpretation of
\If is based on Born's postulate that \If*\If is a probability density, such that \If*\If dr
represents the probability of finding an electron within the volume element dr. This
proposition is reasonable, since l\lfl is the amplitude of a wave, and the intensity of
a wave is proportional to 1\lf1
2
or to \If*\If when \If is a complex quantity. It follows
that
00
I l/Jl/J dr = 1,
00
(5.11)
which is the normalization condition for the wavefunction. Thus, the wavefunction
remains finite over all space. The wavefunction is also continuous and single
valued, so that at any point in space there is a value for \If*\If, and only one such
value. Equation (5.11) imposes the condition on the eigenfunctions described in the
previous sections, that they must be orthonormal, which may be written as
v. d r
)
= (5 ••,
1)
(5.12)
where the integral extends over the range of the variables. If we consider
wavefunctions that are the linear combinations (5.9), then from (5.12) we have
= 0 .._
1)
(5.13)
For this equation to be nonzero we require i = t. then,
I
' c:l/J'», d'r = 1.
L. 1 1 1
1
Reordering the integral and the summation, and using (5.12),
' c ~ = 1,
L. 1
1
(5.14)
(5.15)
Sec. 5.3] An Excursion into Function space III
that is, the sum of the squares of the amounts of each contributing wavefunction in
the linear combination is unity; (5.15) is the normalizing equation for the
coefficients en in (5.9).
5.3 A FURTHER EXCURSION INTO FUNCTION SPACE
We have made implicit use of function space in discussing direct product
representations in Section 4.1.5. A function space may be looked upon as a set of
functions linked by certain rules, somewhat similar to those that we have used in
discussing the manipulations of vectors (see Section 2.5ft). Consider a set of
functions fi, h, .... If these functions span a function space, then certain conditions
hold:
(a) Any function that is a linear combination ofli,h, ... is also a member of the set.
This rule may be compared to that in Section 3.2.I(a).
(b) The scalar product of any two functions is defined by
f of = I ff dr , (5.16)
1 2 1 2
Here, we compare (2.9), which may be generalized to any two vectors rex, y, z) and
r' (x', y', z') such that
1"1" = xx'i +yy'j + zz'k . (5. (7)
For x = x', y =y' and z = z', we obtain (2.10) for r
2
; for I' normal to r' the right
hand side of (5.17) is zero. It follows from (2.2) that
r'(er') = e 1"1" ,
where e is a scalar constant, and from (2.3) that
r·(t + 1") == r·t + 1"1" ,
(5.18)
(5.19)
where t is another vector. The scalar product (5.16) for two functions obeys the
same rules. For example, if fi, .h. and h are three functions and e is a scalar
constant,
fi '(ch +h) = efi 12 +fi 'h .
Iffi = h in (5.16), then
fi 11 = N
2
(5.20)
(5.21)
where N is similar to the magnitude of a position vector. The factor liN is the
normalization constant forfi. More generally, we write
f. of .
1 J
=
I
r'.«,
1 J
= K' ,
(5.22)
if K = 0 the two functions are orthogonal, and if K = I the functions are normalized.
(c) lfthe k functions fi, h. ......fk are linearly independent, other functions may be
written as linear combinations of the k functions; here, we may recall the linear
independence of the orthogonal unit vectors i, .1 and k (Section 2.5.1). We interject
the note that, generally, the functionsfi,h, ..... ft are linearly independent provided
that
112 Group Theory and Wavefunctions
k
\' c.f. = a
L 1 1
i=1
[Ch.5
(5.23)
only when c, := 0 for all values of i.
EXAMPLE 5.1 Suppose that a function space is spanned by the 2p orbitals. We will
examine the scalar products such as Px'px and px'py, where the orbitals are accorded the
formulations:
1
1/ (321ll
1
1/ (327£)
3/2
(Z/a) (Zr/a) exp(Zr/2a ) sin(S) cos(tP)
o 0 0
3/2
(Z/a) (Zr/a) exp(Zr/2a ) sin(S) sin(tP)
000
Using results fromAppendix 5, we write
1 SJOO 4 J7l 3 J27l 2
p.p = () (Zza ) r exp(Zr/a) ar sin (S) dS cos (tP) dtP
X X 327l 0 0
o 0 0
By standard methods (see Appendix 7) the integrals are, in tum, 3/(47t), 4/3 and 7t, so that
their product is unity: p, is a normalized wavefunction (a similar result is obtained for p.),
For the product px'py, we have
p.p = _1_ (Z/a )SJOO r
4
exp(Zr/a ) ar J
7l
s i n
3
(S ) dS J
2
: i n ( 2
tP
) dtP
X Y (327l) 0 0 0 0 0 2
Clearly the third integral is zero, so that px'py is zero; similar results are obtained with the
other p functions. Thus, the function space is spanned by three orthonormal 2p orbitals.
5.3.1 Defining operators in function space
Let a symmetry operation R (see Section 2.2ft) be represented by a transformation
operator OR. A transformation operator operates on the functions of function space,
and follows the rules for linear operators given in Section 2.2. The set of such
operators for all symmetry operations R in a point group is homomorphic (Section
3.2.2) with the set of symmetry operations themselves. If a symmetry operation R
moves a vector from the position r to a new position r', we define the
transformation operator OR associated with R by
ORf{r') := j{r) , (5.24)
that is, the new function OR! assigns the value of the original function f at the
location r to a new location r'; we see that r' is related to r by an equation similar
to (4.4).
We establish next a rule for transformation operators in function space that is
paralleled by a rule for symmetry operations in real space. Consider the symmetry
operations Rand R' in a point group, such that R moves a vector from r to r', and
R' then moves r' to rtf. From the definition of a group, we know that there will be
another symmetry operation R" in the group, given by
R" := R'R
that moves r to '0" directly.
(5.25)
Sec. 5.3] An excursion into function space 113
The associated transformation operator moves a function/defined at r to the new
location r":
(5.28)
(5.26)
(5.29)
(5.27)
(OR·j)(r") = .f(r) .
For another function g in the same space zsf, (5.24) leads to
(OR'g)(r") = g(r') .
Since g is any function, let it be equal to Ow; then, with (5.24),
g(r') = (ORf)(r') = .f(r) .
Applying this result to (5.27), we have
[OdORf)](I''') = g(r') = (ORf)(r') = .f(r)
which, from (5.26), shows that
OR" = OR'OR (5.30)
Thus, the relationship (5.25) for the symmetry operations is paralled by (5.30) for
the corresponding transformation operators.
EXAMPLE 5.2. Consider a function space spanned by the three p orbitals given by (4.29).
The matrix in (4.3) shows that a rotational operation Co moves a vector rex, y, z) to a new
position r'(x',y', z'), where [r] = Ir'l and
x' = x cos(S)  y sin(S),
y' =x sin(S) +y cos(8).
z' =z.
Inverting these equations leads to
x = x' cos(8) +y' sin(8),
y = x' sin(S) +y' cos(8),
z=z'.
Considering first p, the operator Oe that corresponds to the symmetry operation Co has the
property
Oop,{x',y',z') = p.lx,y,z) = j(r)x/r.
Replacing x and r on the extreme righthand side from above gives
Oopx(x',y',z') = j(1/) [x' cos(8) +y' sin(8)]/,..'
Since we have primes on both sides of the equation we can, for neatness, omit them so that
we have finally the equation
OePx (x,y,z) = j(r) [x cos(8) +y sin(8)]/r.
Similar equations can be developed for pyand Pt.
Unitary operators
The righthand side of the last equation in Example 5.2 may be recast, using (4.29),
as
OePx = Pxcos(8) + Pysin(8) + P: x 0 . (5.31)
114
Similarly,
GrOUI) Theory and Wavefunctions rcns
= + P x a
y
+ P x l.
z
(5.32}
(5.33)
As OaPi (i = x, y, z) is a row vector, these equations form the matrix D(C
a):
=
[
cas(S)
sineS)
a
sin(S)
cas(S)
a
~ ].
(5.34)
It is evident that (5.34) shows a formal equivalence to (4.3).
We can now make an important generalization from this equation, but first we
need to introduce a small change of notation, for reasons of convenience that will
be readily apparent. We rename the Px, py and pz orbitals as PI, P2 and P3,
respectively, and the matrix elements as D(R)u. In Section 4.1.2, the operations that
we discussed, in real space, may be summarized in the new notation by
3
Rei = L r
j i
e
i
, (5.35)
j=l
where the unit vectors i, .i and I{ have been relabelled as e., e2 and e3, respectively.
The p orbital transformation in function space is given similarly by
n
oRPi = \ D (R) " n. (5 . 36 )
L )1)
j=l
with n = 3 and i taking the values 13 for the three p orbitals. The Dmatrices that
can arise in this context combine in the same way as their associated symmetry
operators; (5.36) is actually a formalism of the equations that we used in Example
5.2. Thus, by analogy with (5.25),
D(R") = D(R')D(R). (5.37)
From the nature of a scalar. it is evident that transformation operators leave a
scalar product of two functions unchanged:
(5.38)
These operators are said to be unitary and can be represented by unitary matrices
(see Section 2.5.5), which lead to unitary representations for point groups (see
Appendix 6).
If we operate on the wavefunction (5.2) by a symmetry R, we write
(5.39)
so that 0R\j! is an eigenfunction. If \j! is normalized, then 0R\j! will be normalized
provided that
Sec. 5.4] Using Operators with Direct Products 115
OR\j1 = N\l/, (5.40)
where N = ±1. Thus, by operating on \11 with the symmetry operators of a point
group, we obtain a representation with each matrix being either (1) or (1); such a
representation is onedimensional and irreducible. If degeneracy is present among n
solutions of (5.2), then we can write a set of k solutions that have the energy Ea. as
H I/J
=
Eal/J
a
1
a,l a,l ,
H.
I/J
=
Eal/J
a
2
a,2 a,2 ,
(5.41)
H I/J =
Eal/Ja,k
a,k a,k
where the \j!a.J set may be single functions or a linear combination. All k solutions
span a kdimensional function space provided that they are linearly independent.
Consider the operator OR for the symmetry operation R acting upon any of the
above functions, say \j/a..i ; then,
(5.42)
Thus, OR\j!a..i is a solution of (5.2), which means that the set of functions OR\j!a.i (i
= 1,2, ... n) spans a function space of dimension, or degeneracy, n.
5.4 USING OPERATORS WITH DIRECT PRODUCTS
Consider two representations fa. and I' of a point group, formed from basis
functions \j/"'i and ' respectively. From (5.36), we have
n
a
°RI/Ja,i = LDa(R)pi I/Ja,p (5.43)
p=l
n
o I/Ja . = )3Da (R) . I/Ja ' ( 5 . 44 )
R fJ,) L p qj p,q
q=l
where na. and nl). are the dimensions of fa. and respectively. The product
functions \j!a..i form a basis for the direct product fa. ® Using results above,
and with a symmetry operation R, we have
°(I/J . I/Ja .) = °I/J . 0 I/Ja .
R a,1 p,) Ra,1 R p , )
n n
=,a ;J3D (R) . Da(R) . I/J . I/J
a..
(5.45)
L L a p i IJ q) a, I p,)
p=l q=l
Let the n.; products \1''''.1 be ordered and equated to 'P, , where s runs from 1
to (see also Section 4.1.5). Then (5.45) can be recast as
116 Group Theory and Wavefunctions icns
Ow
R S
n
cxn(3
= I Dcx®(3 (R ) t s Wt .
t=l
(5.46)
where sand t represent the pairs of suffixes i j and p,q respectively; then we have
(5.48) X Q (R).
CX®,J
=
D Q(R)
CX®p ss
DCX®Q(R)ts = D (R) ® D (R) . (5.47)
IJ cx pi (3 qj'
these matrix products are discussed sufficiently in Section 4.1.5.
The product functions \1'0..1 \1'1
1
,/ form a basis for a direct product ex. (8) f p in a
given point group, and the characters of the Dmatrices obtained will be of great
importance in our subsequent discussions; they may be found as follows. The
character of R in the product fa. (8) f
ll
is given by summing (5.47) over no.np: with t
= s, the lefthand side becomes
n
cxn(3
I
S=l
The sum over s from 1 to 1100np is equivalent to separate sums in (5.47) over i from 1
to n« and over) from I to nil' Thus, (5.48) may be written in extenso as
n
cx
n(3
I I Dcx(R)ii D(3(R)jj = Xcx(R) X(3(R). (5.49)
i=l j=l
Finally, the combination of (5.48) and (5.49) shows that
=
(5.50)
This equation provides the theoretical justification for the direct products of
representations developed in Section 4.1.5. We can extend (5.50) to more than two
representations. Thus.
(5.51)
also can be a representation of the same point group. For example, consider the
irreducible representations .4
2
, E and T) in T
d
, the character table for which has
been given in Section 4.1.5. We can show that.4
2
(8) E (8) T
1
=.4
2
(8) (E (8) T
I
) = A
2
(8) (T] + T
2
) = T, + T»:
A : 1 1 1 1 1
2
E : 2 1 2 0 0
T: 3 0 1 1 1
1
T: 3 0 1 1 1
2
A ® E ® T: 6 0 2 0 0
 T + T.
2 1
1 2
Sec. 5.5] When do Integrals Vanish 117
5.5 WHEN DO INTEGRALS VANISH
We recall the sine function that we met in Section 1.4. We integrate this function
between the limits of ±1/2:
J1/2 s InI Znkz ) dx = 11 (Zrrk ) [ cos I Zrrkx ) ]1/2 = O. (5.52)
1/2 1/2
The integral will vanish whatever the value of ±pfor the integration limits, because
of the anti symmetry of the sine function across the origin. We say that this type of
function could not span the totally symmetric AI irreducible representation.
Consider next the integral
=
f
t/J t/J dr ,
1 2
(5.53)
where \111 and \112 are wavefunctions. Since the value of the integral I is independent
of molecular orientation, any symmetry operation acting on I is equivalent to the
transformation I ~ I , that is, a product \j/\IV2 can be the basis for the AI irreducible
representation. For example, in point group C
3v
suppose that IVI and \112 span AI and
E respectively; then, we have
E
I
2
1
1
1
o
The product \111\112 is 2 1 0, which has the symmetry of E: Al is not present (AI @
E = E) and the integral (5.53) vanishes because \j/l and \112 do not transform as the
same irreducible representation of the group. Had 11/2 spanned A1 also, then \111 \112
would have had the symmetry of A1 and the integral would not necessarily vanish;
it could, however, vanish for reasons unrelated to symmetry. The arguments can be
extended to products of more than two functions. It follows also that, since the
Hamiltonian operator belongs to the fully symmetric representation of a point group
(see Section 6.1 later), integrals of the type flViR 111}d. can be nonvanishing only if
\IIi and \II) span one and the same irreducible representation in a given point group.
EXAMPLE 5.3. Can the integrals of the functions (a) x
2
l, and (b) xl l + i be non
vanishing when integrated over a square centred at the origin? A square corresponds to the
point group D4h. Hence, from the character table for this point group:
(a) x
2
l spans Big and the integral vanishes.
(b) x
2
l + Z2 spans Big +Alg; the integral can be nonvanishing.
In applications of quantum mechanics to spectroscopy, such as the transition
from a vibrational initial (ground) state Il/i of a molecule to an excited state \IIf, we
encounter integrals of the form
Jt/J; IJ. t/Jf dr,
(5.54)
118 GrOUI) Theory and Wavefunctions icu s
where ~ is a transitional moment operator, the dipole moment operator, for
example. We write the dipole moment operator as
= \' e.r.
L. 1 1
1
= L ej(ix
j
+ jY
j
+ kz
j),
j
(5.55)
where e, is the charge on the ith particle and Xi , Yi and z, are the coordinates of
its position vector rio Hence. (5.54) can be resolved into three integrals, for
example, that along the x axis is
I
I/J fl I/J d'r. (5.56)
i x £
The integral (5.54) will be nonzero if only one of its component integrals like
(5.56) is nonzero: for this to arise, the direct product 'Vt ® 'Vr must give a
representation that contains a component irreducible representation that has the
transformation properties of the function u, or, alternatively, that the direct product
of'Vt , flx and ~ j 1 r contains the fully symmetric representation AI.
The wavefunction in the vibrational ground state ('Vi) has the same mathematical
form as that of an s orbital, so it is spherically (totally) symmetric, which means
that there are no symmetry restrictions attached to it. We will assume a bent,
triatomic molecule belonging to the point group C
2v
, like the water molecule. The
character table shows that x, Y and Z have the symmetries BI, B
2
and AI,
respectively. However, we showed through Problem 4.4 that this molecule had
vibrational (final) states ('Vr) corresponding to A 1 and B
I
symmetries. Thus, the
integral (5.54) is investigated through the following direct products:
® fl/J .
e
(5.57)
With r'Vi = Al and r'Vr= AI. we obtain
Al ® B
I
®A
I
= B
I
,
Al ®B
2®A 1
= B
2
,
A} ®A
I
®A
I
= AI .
and with r 'Vi = A1 and r'Vr = B
2
, we obtain
AI ® B
I
® B
2
= A
2
,
A I ® B
2
® B
2
= A I ,
AI ® AI ® B
2
= B
2
.
Thus, the integral (5.56) can be nonzero in both the Al and B
2
symmetries, because
the direct product contains the fully symmetric Al representation in each case. We
shall meet applications of vanishing integrals in more detail in a later chapter.
Sec. 5.6] Symmetryadapted Linear Combinations 119
5.6 SETTING UP SYMMETRYADAPTED LINEAR COMBINATIONS
In applying group theory to some of the major topics of the remaining chapters of
this book, chemical bonding and ligandfield theory, for example, we need to seek
certain linear combinations of orthonormal wavefunctions and form bases that span
the irreducible representations of given symmetry species of a point group. The
linear combinations so formed are solutions of the wave equation or can be
combined into such solutions, and we may use the symmetry properties of the
functions in accordance with the theory that we have set up in this and previous
chapters. The functions that we shall devise are known as symmetryadapted linear
combinations (SALCs): they are adapted to the symmetry of the molecule, and are
used to build up molecular orbitals. However, we must consider first the topic of
projection operators, which we shall find lead to a straightforward way of setting up
SALCs.
(5.58)
5.6.1 Deriving and using projection operators
Consider a set of orthonormal functions \/lP.I, \/lp,2, ...., \lfp,n, that form a basis for
the Bth, npdimensional irreducible representation f
p
in a given point group of
order h. For any symmetry operator R, we can write from (5.36)
n
;J3D{3 (R) l/J{3'
L pq,p
P=l
Because the basis functions are orthonormal, the Dmatrices will be unitary (see
Section 2.5.5 and Appendix 6). Leftmultiplication by D: (R)ij, from a representa
tion of the same symmetry R followed by a summation over all R, reversing the
order of summation on the righthand side, leads to
(5.59) =
n
;J3 \ D (R) .. D{3 (R) l/J{3'
L L
R
a 1) pq,p
P=l
From the great orthogonality theorem (4.42), the righthand side of (5.59) may be
equated to
\ D (R) .. 0 l/J{3
L
R
a 1) R ,q
n
;J3 h 0 0 0
L 1/n
an{3
a{3 i p jq l/J{3,p'
p=l
which is zero if <X 7= ~ 1 , but which, for Ct. = 13, gives (h/na.)8,q \/la.i because the sum
over p is zero except for p = i. Thus, (5.59) may be written as
P .. l/J{3
a,l) ,q
=
!2 0 o.·J.
n a{3 ia re. r:
a
(5.60)
where
P ..
a,l)
(5.61)
120 GrOUJl Theory and Wavefunctions rcns
and is known as a projection operator. Evidently, it is a linear combination of
operators OR with coefficients from the Dmatrices of the representation r 0.'
If we consider the nonzero case of (5.60) with a = 13 andj =q, we can write
h
P .. l/J . = _.1. (5. 62 )
a, 1 J a, J n 'I'«. i.'
a '
so that Po.,ij operating on the function \1'0. at the location j reproduces that function,
multiplied by hlno., at a new location i.
We can define another projection operator Po. that is a linear combination, having
the same properties as those just described, by using the matrix elements from
(5.61) for the special case of i =j:
n n
a a
LD:(R)ij
P =
L
P =
L
o·
a
a, ii
R'
i=l
R
i=l
(5.63)
(5.64)
since L.iD: (R); = X: (R), we sum first over i to obtain
P = \;/(R)0,
a L a R
R
where the coefficient of OR is the complex conjugate of the character of R in the
representation r 0.' Where the characters are real, X:, (R) is replaced by Xo.(R). We
see that whereas the use of (5.61) needs the complete Dmatrix in order to define
the projection operator Po..!! ' we can obtain Po. very readily from the character table
of a point group. From (5.59) and (5.60) with i = j,
i=l
For a *' ~ , P0.\1/0.,1 is zero. but for ex. = ~ " \ (and i = q)
=
n
a h
L n
a
o s . l/J{3"
a{3 iq ,1
(5.65)
=
(5.66)
The projection operator Po. acting on a function that is a member of the r 0. function
space reproduces that function multiplied by hlno., but any function not belonging to
the r 0. function space is annihilated. The operator Po. may be applied to any linear
combination of basis functions in the space r 0.' Thus, from a linear combination
P",'II", = (h/n) \ ;./ (R) °'II ,
...... a LaRa
R
we find
=
... , c l/J
n a,n
(5.67)
(5.68)
Sec. 5.6] Symmetry and Adapted Linear Combinations 121
where '¥(J. is given by (5.67). Thus, P(J. generates a sum of members of a basis set
spanning the irreducible representation r (J..
EXAMPLE 5.4 We explore the application of projection operators first with point group C3v.
We choose a basis of orbitals a. (spanning AI), 13 (spanning A2), and 11, v (spanning the two
dimensional E representation). Referring to the extended character table for C3v in Example
4.4, we can now consider the effect of each ORon these orbitals (remember that they behave
like row vectors).
We tabulate the effect of each operation on the basis; all entries in the table are the values of
OR/, wherefis one of a., 13, 11 or v.
The projection operators for C3v may be then written down from the character table (all
characters are real) and (5.64):
0 0 o 2 0 o ,
o "
E C C
(J (J (J
3 3 v v v
a a a a a a a
13 13 13 13 13 13 13
13
)(
JL JL
2
JL
(V3
(V3
v v
'2
JL v
'2
JL
We examine now the effect of these projection operators on the four functions, a, 13, Jl and
v, using the table prepared above:
P
A
a a + a + a + a + a + a 6a
1
P
A
a a + a + a  a  a  a 0
2
P
E
a 2a  a  a 0
We see that PAl operating on ex, a function spanning AI, multiplies it by (hln
a
) , or 6, but
with P.42 or PE the function ex is annihilated. If we explore the other irreducible
representations, similar results are obtained. For 13, we have:
P
A
13 13 + 13 + 13 + (13> + (13> + (13> 0
1
PA (3
(3 + (3 + (3  ((3>  ((3>  ((3> 6(3
2
P
E
(3 2(3  (3  (3 0
For 11, the equations become:
PA JL
JL +
(
+
(
V;v)
1
+ JL +
+
0
122 Group Theory and Wavefunctions rcns
f.l +
+ (f.ll
= 2f.l 
(
(
+
(
o
E is a twodimensional representation, so that h/no. = 3. Finally, for v, we have:
v +
+ (Vl +
v +
 (Vl 
2v 
+
+
+

o
o
3v
EXAMPLE 5.5. We consider the irreducible representations spanned by p orbitals in point
group C4v. In the diagram below, the C
4
rotation axis (z) is normal to x and y, and the
(vertical) crv and crd planes are indicated. The px, py and pz orbitals lie along the
corresponding axes, and the character table for C4v is also given.
t5' E
4v
A 1
1
A 1
2
B 1
1
B 1
2
E 2
C C
3 C
cry
442
1 1 1 1
1 1 1 1
1 1 1 1
1 1 1 1
o 0 2 0
\
\
\
1 1 1
1 1 1
1 1 1
1 1 1
o 0 0
(J"
d
x, (J'
v
y, (J"
v
Sec. 5.6] Symmetryadapted Linear Combinations 123
From the diagram, we tabulate the effect on the p orbitals of ORP, when applied with each of
the symmetry operators in point group C4v :
o
E
o
C
4
o 3 0 0
C4 C
2
cry
o ,
cr
d
p
y
py py px px py py py px px
pz pz pz pz pz pz pz pz pz
We use (5.36) now with this table to obtain the diagonal elements of the Dmatrices that
represent C4v in the p orbital basis, form the sum for each operator, and so obtain the
representation
fred 3 I or fred
3 I I I
which may be reduced by standard methods (see Section 4.4) to Al + E. Note that in the
column OC4 , for example, px+ pyand py+ px. Hence, these terms contribute zero to XC4,
whereas pz + pzand makes a finite contribution, of 1.
In order to associate the individual p orbitals with the irreducible representations, we
apply the projection operator (5.64) in the forms PAl and PE . Thus,
PAIPx = px + py  py  P
x
+ px  p, + py  py = 0
Similarly,PAIP
y
= 0, but for PA1pz we have
PAIpz = pz + pz + pz + pz + Pz + pz + pz + pz = Sp,
When we use P
E
we find PE pz= 0, but for PE pxwe have
PEpx = Zp,  2(px) = 4px
and, in a similar manner, PEPy = 4py. Thus, A, is spanned by pz, and E by the degenerate pair
pxand py. The effect of PAl on the function pz is to multiply pz by (hlnA) ), or 8. In the case
of PEPx or PEPy the multiplying factor MilE is 4, because E is a doublydegenerate
irreducible representation. Thus, z spans AI and the x, y pair span the doublydegenerate E
representation.
5.6.2 Deriving symmetryadapted orbitals for the carbonate ion
The carbonate ion [C0
3
f belongs to point group D
3h
, and we consider orbitals on
the oxygen atoms that lie along the CO abond directions shown in Figure S.la;
they may be regarded as combinations of s, p, and py, and their positive lobes all
point to the carbon atom; the character table for D
3h
is reproduced below.
D
3h
E 2C
3
3C; crb 25
3
3a
v
A' 1 1 1 1 1 1
1
A' 1 1 1 1 1 1
2
E' 2 1 a 2 1 a
A' ,
1 1 1 1 1 1
1
A I I
1 1 1 1 1 1
2
EI I
2 1 a 2 1 a
124 GI"OUI) Theory and Wavefunctions icns
Following previous arguments, we can use these orbitals to form a representation.
By considering the effect of each class of symmetry operation of D
3h
on the orbitals
of the oxygen atoms, we find a representation Cod, which reduces to A ~ + E':
D
3h
E 2C
3
3C ~ O"h 28
3
30"v
Cod 3 0 1 3 0 1
At this stage we enumerate the first of two useful rules that derive from the
discussion in Section 4.1ff.
Rule 1. The characters of a representation, on a basis set of orbitals, can be
determined from the fact that the matrix trace LiD(R)ij, or x(R)ij, for a symmetry
operation Rgains contributions asfollows:
If the orbital is mapped on to itselfby R +1
Ifthe orbital is moved to a new site by R 0
If the orbital is inverted on its own site by R 1.
Next we apply the operators PA~ and PH' to every individual symmetry operation.
Following (5.68), remembering that all characters are real, we use
Po. = LRXo.(R)OR;
calling the orbitals on the oxygen atoms 0
1
, O
2
and 0
3
, we obtain
P
A,
Q = (l)Q + (l)Q + (l)Q + (1) (Q ) + (1) (Q )
2
1
1 2 3 1 3
+ (l)(Q ) + (l)Q + (l)Q + (1)Q + (1)Q
2 1 2 3 1
+ (l)Q + (l)Q = 2(Q + Q + Q). (5.69)
3 2 1 2 3
As well as using an orthonormal basis (see Section 5.3), we require the symmetry
adapted orbitals to be orthonormal. We can neglect the factor 2 in (5.69), and the
factor (hln.; ) from (5.68), because they will be incorporated into the subsequent
normalization process. Using (5.12), noting that (0], 0.
2
and 0.
3
) is real, and
assuming no overlap between these 0" orbitals, we normalize (5.69) as follows:
8 ' O ~ _ , , ~ ~
°1
', <, CO + CO
, ............... 3 2
' ~   "
B b
Fig.5.1 rr Orbitals of oxygen in the [C0
3
f ion. (a) The rr orbitals lie along the co bond
directions, in the cr
v
planes; C
3
is normal to the molecular plane and 3C~ lie along the co
bond directions. Vector CO] indicates the x axis, so vector COJ + CO
2
is orthogonal to x.
(b) Outofplane p orbitals of oxygen.
Sec. 5.6] Symmetryadapted Linear Combinations 125
J
(Q + Q + Q )(Q + Q + Q ) dT = J(Q2
1
+ n
2
n
2
) d
1 2 3 1 2 3 U
2
+ u
3
T
= 3, (5.70)
because all terms f .o;.o
j
dr (i 7= j) equate to zero; we obtain for A ~ the normalized
function, (l/J3)(.o
I
+ .0
2
+ .0
3
) . If we had retained the factor 2, from (5.69), we
would have had to multiply (5.70) by 2
2
: but then, the normalization factor would
have been l/(2J3), leading to the same final function.
By similar procedures we find PH' .0 = 2(2.0
1
 .0
2
 .0
3
) , and the normalized E'
representation becomes (l/J6) (2.0,  .0
2
 .0
3
) . However, a second function is
needed to complete the representation.
Generating a second function for a degenerate representation
If we use the projection operator PH' on O, and .0
3
we obtain (1/J6)(2.o
2
 .0
3
 .od
and (l/J6)(2.o
3
 .0
1
 .0
2
) , respectively. These normalized functions, together with
PH' .0
1
, are not linearly independent because their sum is zero. In addition, although
they are, themselves, orthonormal, they are not orthonormal to the first two
functions developed. The reason is that the o orbitals lie along the three Co bond
directions (Figure 5.la), and this feature is transmitted to the functions themselves.
If we assume that the bond vector CO} is the x axis, then we need a linear
combination that is orthogonal to it. We can see that. vectorially, (C0
3
+ CO
2
) is
such a combination. Hence. we have PH' (.0
3
+ .0
2
) = (2.0
3
.o}  .0
2
) + (2.0
2
 .0
3
 .od = 3.0
2
 3.0
3
. Normalizing (.0
2
 .0
3
) leads to (l/J2)(.o
2
 .0
3
) . It may be
shown readily that the resulting set of functions is orthonormal:
A': (1Iv'3)(Q + Q + Q)
2 123
{
(1/v'6)(ZQ  Q  Q )
£': 1 2 3
(l/v'Z)(Q Q)
We now establish and illustrate the s e c ~ n d of tTle two rules for forming symmetry
adapted orbitals.
Rule 2. We may construct symmetryadapted orbitals in a given point group by
employing an appropriate rotation subgroup a/that point group.
For example, with the carbonate ion (D
3h
) , we may use the point group C
3
, the
character table for which is shown below:
E C C
2
e = exp( iZnl3)
C3 3 3
A 1
1
1
1
•
c
1
•
e
Comparison of this table with that for D
3h
shows that the characters under E, C3
and C ~ (2C
3
) of the A and Etype representations are the same in both point
groups. Using now C
3
, and working as before, we generate the representation
126 Group Theory and Wavefunctions [Ch.5
Normalized
•
Q + c Q + eQ
123
•
Q + eQ + e Q
1 2 3
P
E
Q
1
b
We can eliminate the complex numbers by taking the sum and difference, (PEPl
 PEpl )/i, of these two E functions (the ...J3 factor is absorbed in the
normalization), leading to the SALCs:
Sum
ZQ  Q  Q
123
Difference
en  Q )
2 3
(1/v6) (ZQ  Q  Q )
1 2 3
Normalized
(1/vZ) en  Q )
2 3
Thus, we have achieved the same results as with D
3h
but using significantly less
effort.
Of the 24 electrons in the L shell of the [C0
3
f ion, 6 occupy the three c
molecular orbitals (also called po) and 12 reside as six lone pairs on the oxygen
atoms. The remaining six pz electrons form 1t (p1t) molecular orbitals with the pz
orbital of carbon. Figure 5.lb shows the outofplane p orbitals: the reader is invited
to determine the irreducible representations and SALCs for the p1t bonds in the
carbonate ion.
5.6.3 Handling complex characters
Consider the point group 54. It is Abelian with order 4: there are four classes
because 8
4
and 8 ~ do not combine into one class in this point group: the reader
may wish to evaluate the similarity transformations C 2
1
8
4C2
and C 2
1
8 ~ C
2
,
where C 2
1
= C
2
and
[
1 a 0]
c = a 1 a ,
2 a a 1
s = [ ~  ~ ~ ] .
4 a 01
Thus there are four onedimensional irreducible representations, [1 ~ [4, which
need to be orthonormal. From (4.42), with i = P and} = q, we have, since n« = n ~ =
1 for onedimensional representations,
4
\' D· (R) ..D{3(R) ..
L (X 1) 1)
i=l
=
(5.71)
Sec. 5.6] Symmetry and Adapted Linear Combinations 127
and the representations C (r = 14) will obey this equation.
Ifwe let exp(i2rn/4) (= exp(irn/2)) = 6
r
, we can begin to write the character table
for point group 54 by setting down the first column and then obtaining the
remaining terms by multiplication, since they are multiples of S4: 54 is a cyclic
group.
We know that exp(intl2) may be expanded by de Moivre's theorem:
exp(irn/2) = cos(rnl2) + i sin(rn/2) , (5.72)
so that the relationships between powers of 6 can be obtained.
5 52 53 54
4 4 4 4
r
1
r
2
r
3
r
4
e
2
e
3
e
4
e
234
£ £ £
468
£ £ £
6 9 12
£ £ £
8 12 16
£ £ £
r
r
r
e
r
e
1, 9
i
3
i
2, 6
1
4, 8, 12, 16 1
Thus, the character table may be written initially as
54 S4 S; S ~
[1 Ii
[2 I 1 I
[3 i I
[4 I
S·
•
1
1
I
I
The table is beginning to assume a recognizable form. We recall that S: = E and
S ~ = C
2
, so we reorder and relabel the entries according to the rules given earlier,
add the other columns (see Problem 5.13), and so obtain
E 5 C 53
54 4 2 4
2 2 2
A 1 1
1 1 R
z ; x +y
Z
2 2
B 1 1
1 1
z
x y ; xy
{
1 i 1
i
}
E
(yz, zx)
1
i 1
i
(x , y) ; (R , R
)
x
Y
In the two onedimensional representations bracketed as E, the characters in the
second of them are the complex conjugates of those in the first. Procedures such as
128 Group Theory and Wavefunctions [Ch.5
those employed in Examples 5.3 and 5.4 may be used to complete the function parts
ofthe table.
The majority of point groups have character tables with real characters. A few of
them contain complex characters: C
n
and C
nh
(n > 2), ~ n , T and T
h
• They arise
naturally through the great orthogonality theorem, as we have just seen. In most
point groups, the degenerate representations have real characters; in others, those
indicated above, the two onedimensional representations are often added, character
by character, to produce real characters. Thus, for 54 we could write:
54 E 5 C
53
4 2 4
E
{
1 i 1 i
1 i 1 i
E 2 0 2 0
In some applications, such as molecularorbital symmetries and selections rules,
this formulation is satisfactory, but in reducing a representation by (4.64) an
erroneous result can be obtained.
Consider the dihydrogenphosphate ion, [H
Z
P0
4
L which we illustrated in Figure
2.4. Ifwe set up a representation with the PO bond directions as a basis, we obtain
~ E S4 Cz S ~
fred I 4 0 0 0
If we reduce this representation according to (4.64), taking E as a single two
dimensional representation, we obtain
fred =A + B + 2E
which is clearly erroneous, since the result does not obey several of the equations
(4.65)(4.70). (See also Example 4.9.) What is the correct result here?
PROBLEMS 5
5.1 Formulate the wave equation for the electrons in the helium atom. (Do not
attempt to solve it.)
5.2 (a) Normalize the oneelectron wavefunction \jJ = exp(r/a
o
) , where a., is the
Bohr radius, 52.9 pm. (b) What is the probability of finding the electron within
a spherical shell of thickness 1 pm at distances (i) 1 pm from nucleus, and (ii)
52.9 pm from the nucleus?
5.3 What is the resultant of LX«(R)XIl(R) for each of the following cases?
(a) C
4v
, ex = /3 = B\; (b) D
4h
, ex =A
zg
, /3 =A
zu
;
(c) D
3h
, ex = /3 =E'; (d) T
h
, ex =ex =T
z
.
5.4 (a) Which of the 2s and 2p orbitals of nitrogen can have a nonzero overlap
integral with the Is orbital of hydrogen in ammonia (C
3v
)? With what orbital
can N(2s) be nonvanishing? How does the N(2pz)H(ls) overlap result vary
with the HNH bond angle? It may be useful to note that the transformations
Problems 129
needed for the ammonia molecule are the same as those for the carbonate ion;
only the irreducible representations differ.
(b) Does fd
xy
Z d
x2

y2
dr vanish under C
4v?
2
 Y
~ zx
2
oc X
d
2
d
5
d ~ xy
4
For point group C
4v
, deduce a representation on the basis of the five d orbitals,
and determine the irreducible representations that they span, given the
following five functions:
d ~ 3z
2
_ r
2
, or 2z
2
_ x
2
_ y2
1
d ~ yz
3
5.5
o
o 0 0 12 0 4
5.6 Construct symmetry adapted orbitals from the outofplane, pzorbitals of
fluorine in xenon terafluoride XeF
4
, point group D
4h
5.7 Determine the direct products between all irreducible representations in (a) C
2h,
and (b) r;
5.8 Reduce the following representations:
(a) C
4v
: Ced = 4 0 0 0 2
(b) D
4d
: [red = 6 0 2 0 2 0
(c) D
6h
: Ced = 30 4 0 2 2 2
A program RD6H is available on the Web site www.horwood.netlpublish that
reduces a representation in D
6h
. Can you modify the Fortran77 program
(RD6H.FOR) for another point group, such as C
4v
?
5.9 Deduce a representation for cyanuric triazide, point group C
3h
(see Problem
Llc), using the pz orbitals on the ring atoms as a basis; they lie normal to the
ring. Then, reduce the representation.
5.tO Methane CH
4
belongs to point group T
d
. (a) What irreducible representations
are spanned by the hydrogen Is orbitals? (b) What orbitals can the carbon
atom use in bonding with hydrogen in methane? (c) Could the d orbitals of
carbon contribute to the bonding in this species?
5.11 (a) What is the point group of transI,2dichloroethene? (b) What are the
characters of the reducible representations that have as a basis (i) the
hydrogen Is orbitals, and (ii) the chlorine 2p orbitals in this species? (Let the
molecular plane be xv.) Reduce the representations into their components.
5.12 In the octahedral coordination compound [Co(NH
2CH2CH2NH2)3]Ch,
the
diaminoethene ligands are bonded through the nitrogen atoms to adjacent
coordination sites on the cobalt atom. What is the symmetry of the complex
ion? Would it be expected to be optically active?
5.t3 Justify the entries in columns 3 and 4 of the character table for C:zh (see
Appendix 11).
6
Group theory and chemical bonding
There are science and the applications
ofscience, bound together as the fruit
ofthe tree which bears it.
L Pasteur (18221895): Revue Scientifique, 1871
6.1 INTRODUCTION: MOLECULAR ORBITALS
In this chapter we shall consider how symmetry and group theory may be used to
simplify the study of the molecularorbital theory of chemical bonding. We shall be
concerned mainly with organic molecules, for which we shall develop the Huckel
molecularorbital theory, and transitionmetal compounds with which we shall
introduce crystalfield and ligandfield theories.
A molecular orbital (MO) may be considered to be built up from a combination of
atomic orbitals (AOs), and to extend over the whole molecule. Thus, electrons may
be delocalized around the molecule, and arc subject to the symmetry of the
molecule, its point group.
Molecular orbitals, like atomic orbitals, arc mathematical functions, but it is
convenient to have also a pictorial description of them by defining boundary
surfaces that enclose a certain fraction, say 90%, of their electron density, as with
atomic orbitals. Figure 6.1 shows some typical atomic and molecular orbitals
relevant to diatomic molecules.
Classifying molecular orbitals by symmetry
It is apparent at once, from Figure 6.1, that molecular orbitals have specific
symmetry properties, and we can set up the following general classification.
(a) Molecular orbitals that are symmetric about the internuclear axis are called o
orbitals, Figure 6.lad.
(b) Molecular orbitals that have a nodal plane (symmetry plane) containing the
internuclear axis are termed t: orbitals, Figure 6.lef. A nodal plane is a region over
which the electron density probability is zero; the xy plane of a pz orbital is an
example of a nodal plane.
Sec. 6.1] Molecular orbitals 131
888
88
I.J
If I
Fig. 6.1 Polar diagrams of atomic orbitals and the molecular orbitals that they form by
overlap. (a) s AOs and O'g (sag) bonding MO; (b) s AOs and au (sO'u) antibonding MO; (c) p
AOs and O'g (PO'g) bonding MO; (d) p AOs and all (pall) antibonding MO; (e) p AOs and Xu
(px
u)
bonding MO; (f) P AOs and 1tg (p1tg) antibonding MO.
(c) Molecular orbitals may be denoted even 'g ' or odd 'u' with respect to the
operation of inversion acting at the centroid of the molecule (centre of symmetry),
and the subscripts' g' and 'u' are known as the parity of the orbital, Figure 6.1a,c,e
(see also Section 4.2.2). The O'g and TC
u
molecular orbitals lead to bond formation
and are called bonding molecular orbitals, whereas o., and TC
g
are anti bonding
molecular orbitals.
Function of the Schrddinger equation
The fundamental starting point for setting up a molecular orbital is the Schrodinger
equation. If we assume that only electrostatic forces are operating, between electrons
and nuclei and between electrons and other electrons. then we can write the
electronic Hamiltonian in the form
H =
\'  ~ V ~ + \' V . + \' V ."
L . 2f..L 1 L . nuc 1, 1 L . e 1ec, 1 , J
1 1 1
(6.1)
The first term on the righthand side represents the kineticenergy operator for the
electrons, the second term is the potentialenergy operator for the interactions of the
electrons and nuclei; both of these terms are summed over the total number n of
132 Group theory and chemical honding [Ch.6
electrons. The third term is the electronic potential energy, summed over ~ (n  I)
2
pairs of electrons: the motion of an electron involves all other electrons, and it is the
resultant mutual interactions that are responsible for the difficulty in solving the
Schrodinger equation exactly. We will assume here that we can replace this term by
one which takes account of the interaction between an electron and a steadystate
electric field of the other electrons; this approach is known as the selfconsistent
field approximation, and leads to the effective Hamilton, which we indicate by 11".
Exact molecular orbitals are eigenfunctions of the Hamiltonian which, itself,
commutes with transformation operators OR for any point group. We have stated
that the Hamiltonian belongs to the fully symmetric representation A1, which we can
show now as follows.
Consider a set of orthonormal functions <Pa.,/ that span the irreducible
representation I'().. Then, from (5.58),
and using (5.6)
= \ D (R)k' 4> k'
L
k
a J a,
(6.2)
0 H
4>a,j
=
H 0
4>a,j R 0 0 R
=
H
o
L D (R) . 4>
k a k.] «.):
=
L D (R)k .(11 4> k)' (6.3)
k a J 0 a,
so that the (H, <P().,,) functions also span F,z Invoking the result of (5.22), we have the
general case
=
(6.4)
which is zero unless 1= j. Taking the direct product I'a: ® fH where fH = (II" <P<X.J)'
then since the H, <Pa.j' functions span I'cc it follows that I'a: ® fH = I'a Thus, fH must
be the fully symmetric representation AI, for which XR = I for all symmetry
operations R.
In applying the molecularorbital method to molecules, it is possible to introduce
approximations at several different levels. We assume that it is valid to describe the
molecular electronic wavefunction by molecular orbitals, that a molecular orbital
can be formed by a linear combination of atomic orbitals, and that we can treat o
bonding and 7t bonding separately. A further approximation about 7t molecular
orbitals leads into the Huckel molecularorbital theory. We shall begin this study
with further considerations of the linear combination of atomic orbitals (LCAO)
approximation.
6.2 SETTING UP LCAO APPROXIMATIONS
An atomic wavefunction consists of a spatial part and a spin part: thus, the ground
state Is wavefunction for the hydrogen atom may be written as
Sec. 6.2] Setting up LCAO approximations 133
t/J = (1/ 3) 1/2
ls,+1/2 na exp(r/a) a
a a '
(6.5)
(6.7)
(6.6)
where ex denotes a spin (m,) of +Y2, one of the two possible values for an electron.
When the atomic orbital is fully occupied, by two electrons, the spins are said to be
paired (±Y2),in accordance with the Pauli exclusion principle.
The LCAD approximation for molecules treats the spatial part of an atomic
wavefunction, and we write the ith molecular orbital <Pi as
¢J
1
· = \ c .. v;
L
j
1J J
where the set of atomic orbitals \111 is orthonormal, that is,
J
t/J ~ v. d'r = <3 ••,
1 J 1J
and the terms cij are linear coefficients. governed by (5.15), with the sum taken over
j terms for the ith molecular orbital.
Like exact molecular orbitals, the LCAD molecular orbitals generate irreducible
representations of the point group of a given molecule; any set of atomic orbitals
that forms a basis for an LCAD molecular orbital will lead to a representation [red
that will, normally, be reducible to a sum of n1dimensional irreducible
representations [1, plus n2dil11ensional representations [2, and so on.
Introducing the variation principle
In order to determine the energy of the ith molecular orbital, we write its wave
equation in the form
H., <P; = lEi <p,. (6.8)
We now apply the variation principle by leftmultiplying this equation by <P/,
integrating over all variables and rearranging the equation to obtain an expression
for £, ; the result will, in general, be larger (more positive) than the true energy £;.0:
J
•
¢J • If ¢J. d'r
J 0 1
(6.9)
E. =
~
£
1
J¢J •• ¢J. dr
i,a
J 1
We introduce the linear combination (6.6) into (6.8) and, for convenience and
without loss of generality, we shall restrict the sum over k to the values 1 and 2.
Hence, for a diatomic molecule we write molecular wavefunctions as
= C .1. + C ,/0
11'1'1 12'1'2
= C .1. + C ./0
21'1'1 22'1'2
}.
(6.10)
We introduce the first of these wavefunctions into (6.9), noting that the
wavefunctions \11 are real, whereupon the integrals become
134 Group theory and chemical bonding rcns
2
= C
11
H l/J dr
o 1
+ 2c c Il/J H' l/J d'r + c
2
I l/J H l/J dr
11 12 1 0 2 12 2 0 2 '
since J l/JI.HOl/J. dr = J l/J.H l/J. dr. Furthermore,
J J o 1
I
(c l/J + c l/J) (c l/J + c l/J ) d'r = c
2
I
11 1 12 2 11 1 12 2 11
+ 2C
11C12
I l/J
1
l/J
2
d'r + C:
2
I l/J
2
l/J
2
dr ,
because J l/Jil/J
j
dr = J l/Jjl/J
i
dr.
(6.11)
l/J
1
l/J
1
dr
(6.12)
We digress for a moment to consider the nature of the integrals in (6.11) and (6.12).
6.2.1 Defining overlap integrals
The integral J\jl ~ \Vi dt, which we shall symbolize as Sij, is known as an overlap
integral. It measures the extent to which two atomic orbitals overlap. Typically,
values of Sij (i ~ j) range from 0.2 to 0.3; Figure 6.2 shows differing degrees of
overlap among Is and 2p orbitals. An overlap that leads to a zero value of Sij , as in
Figure 6.2d, means that the ith andjth orbitals are orthogonal: two different atomic
orbitals on one and the same atom are always orthogonal; bonding overlap takes
(c)
v, IJIj
!bICD
v, IJIj
Idl(]
Fig. 6.2 Overlap of atomic orbitals \11; and \11; . (a) Two separated s orbitals; Sij = O. (b)
Overlap of\jl; and \F); Sij is finite hut small. (c) Overlap Of\jli and \jI); Sij is finite and large.
(d) Overlap of s (\jIi ) and p (\jl) ) where p does not lie along the molecular axis; Sij = 0;
because of the opposing signs for the p orbital overlap.
place only between species of the same symmetry. The calculation of overlap
integrals is complex and not our main concern. However. an indication of the
calculation in the simple case of two hydrogen Is orbitals is given in Appendix 8.
6.2.2 Defining Coulomb and resonance integrals
The integral hv ~ H, \lli dr, which we shall indicate by Hij , may be divided into two
types. For i = j the integral is known as the Coulomb integral a; it may be
Sec. 6.2] Setting up LCAO approximations 135
interpreted as the energy of an electron when it occupies its own orbital. When i ;:f; j,
Hi} is termed the resonance integral ~ , a name that arises on account of a
mechanical analogy which is invalid in this context but is, nevertheless, retained;
both ex. and ~ are negative quantities.
Continuing with the variation principle
It is conventional to make the following substitutions:
J
•
r/J
i
H
o
r/J
j
d't = H. .,
1)
J
•
r/J
j
r/J
j
d't = s ..'
1)
Hence, (6.11)(6.12) become
(6.13)
(6.14)
+ c
2
H
12 22'
+ c
2
S
12 22
(6.15)
+ c
2
H
12 22
+ c
2
S
12 22
c
2
S + 2c c S
11 11 11 12 12
=
c
2
H + 2c c H
11 11 11 12 12
c
2
S + 2c c S
11 11 11 12 12
and we write for the energy
c
2
H + 2c c H
11 11 11 12 12
The values needed for CII and C12 are those that lead to a minimum in E. Thus, we
form the derivatives (aEJ8c
l1
) and (aE/Bcd and set them to zero, whereupon we
obtain the secular equations:
c (H
11 11
c (H
11 21
£.S ) + c (H  £.S ) = a
11 12 12 12
~ S ) + c (H f:S) = a
)'' 12 12 22 22
}.
(6.16)
Sets of such simultaneous equations have nontrivial (nonzero) solutions if the
secular determinant is zero, that is, if
(H
11
ES ) (H  E.S )
11 12 12
= o.
(6.17)
(H ES) (H  £. S )
21 12 22 22
This equation may be simplified if we make the following approximations:
Sji = 1 (6.18)
H
ii
= ex. (6.19)
Hi} = ~ (6.20)
If the molecule for which we have set up (6.10) is a homonuclear diatomic, then
making the substitutions (6.18)(6.20), with ex.j = ex.2 = c, (6.17) may be expanded to
the quadratic
2 )2
(a  E)  «(3  E S
12
= 0,
(6.21)
136 Group theory and chemical bonding [eh.6
which is solved readily to give two solutions for £:
£ ::: (0: + (3)/(1 + S I,
+ 12
(6.22)
£. = (a   5 ). (6.23)
12
The ratio of CII/C)2 follows immediately from (6.16), or from symmetry with a
homonuclear diatomic, as
(6.24)
Now, we normalize (6.10). Let the normalizing constants be N±; then, from (6.10),
incorporating the value of CII into the normalization constant, we have
Thus,
I (t/J ± t/J )2 d'r
=
1. (6.25)
 1 2
t/J2
dc + I dc ± 2I t/J
1
t/J
2
dc1 =
1
1
=
N
2(2
± 25
12
) . (6.26)
±
so that we obtain
¢+
= (2
+ 25 )1/2(t/J
+ t/J2)'
12 1
(6.27)
¢ = (2 25 )l/2(t/J
t/J2) . 
12 1
(6.28)
We could have approached the secular equations in a slightly different manner. We
begin by substituting the first wavefunction 4>, of (6.10) into (6.8):
(6.29)
Leftmultiplying each term of (6.29) by \/11 (strictly, \/1 ), and integrating over all
spatial variables, we obtain
c I t/J (H  £.)t/J dr + c It/J (H  f:)t/J d'r = O. (6.30)
11 1 U 1 12 1 0 2
We make the conventional substitutions (6.13)(6.14) to give
c (H £.5 )
+ c (H  £.5' )
= 0,
(6.31)
11 11 11
12 12 . 12
Now substitute 4>2 from (6.10) into (6.8) and leftmultiply by
\1/2, following
(6.30)(6.31), to give
c I t/J (H  £.) t/J dr +
C
22
It/J
2
( H
o
 .1E.)t/J2 dr = O. (6.32)
21 2 0 . 1
Proceeding as before, we obtain
c (H  £.S ) + c (H  f:5 ) = O.
21 21 21 22 22 22
(6.33)
Sec. 6.2]
Setting up LCAO approximations
137
which, with (6.32), leads immediately to the secular determinant (6.17). The
substitutions of (6.18)(6.20), together with (1,1 = (1,2 = (1, and 8
21
= 8
12
, lead to
equations (6.22)(6.23) for L and L
The general linear combination of n wavefunctions leads to secular equations for the
ith molecular orbital (Cj == c)i ) in the form
c (H £.S ) + c (H £.S ) +
1 11 1 11 2 12 1 12
+ c (H  £.S ) = 0,
n i n 1 s n
c (H ,£.S ) + c (H £.S ) +
1 21 1 21 2 22 1 22
+ c (H £.S )
n an 1 an
0,
c (H £. S )+ c (H E..S ) +
1 rn 1 rn 2 nz 1 nz
+ c (H  £.$ ) = O.
n nn 1 nn
(6.34)
for which the corresponding secular determinant becomes
H  E.S H  £.S H  E.S
11 1 11 12 1 12 1n 1 1n
H  £.S H  E.S H 
£.S
21 1 21 22 1 22 2n 1 2n
O.
=
H  £.S H  £.S H  E.$
(6.35) n1 1 rn n2 1 n2 nn 1 nn
We require that the secular determinant (6.35) shall be zero for nontrivial solutions
of the Cj values. The calculation of the LeAO coefficients by two alternative
procedures is discussed in detail in Appendix 9.
6.2.3 Applying the LCAO method to the oxygen molecule
We apply results from the previous section first to a discussion of the bonding in
molecular oxygen. The ground state electronic configuration for an oxygen atom is
(ls)2 (2S)2 (2p)4; we remember that the 2p orbitals are occupied singly as far as
possible, in accordance with Hund's rule. Like all homonuclear diatomic molecules,
its point group is D"'h, with the character table below:
138 Group theory and chemical bonding [eh.6
1 1
1 1
1 1
1 1
(x , y)
z
C'
2
1
1
o
o
o
1
o
o
o
1
Z cos(¢)
zsl{)
00
2 Z cos(¢)
Z 2 cos(Z¢)
Z
Z Z cos(3¢)
Z Z cos(3¢)
Z Z cos(Z¢)
1
o
o
o
1
o
o
o
1
1
.D E
ZCCP
ooh 00
r+ (A
) 1 1
9 19
r (A )
1 1
9 2g
IT (E )
Z Zcos(¢)
9 19
11 (E )
Z Zcos(Z¢)
9
2g
<P (E ) Z Zcos(3¢)
9 3g
r+ (A )
1 1
u 1u
r

(A )
1 1
u 2u
IT (E )
Z Zcos(¢)
u 1u
11 (E )
Z Zcos(Z¢)
u 2u
<P (E 2 Zcos(3¢)
u : 3u)
We choose the z axis to correspond with the internuclear (Coo) axis, and align two pz
orbitals along it such that their positive regions are adjacent, Figure 6.lc; this
situation achieves a o bond overlap as the two orbitals are brought together to form
a cr
g
molecular orbital. We can see from the diagrams how the symmetry operations
of DOOh will affect the molecular orbital. If we regard the two pz orbitals as distinct,
we have the following results of operating on them with the symmetry operations of
Dooh:
Ep . or
Cl{)
or cr p .
=
Pz,j
U =
1, Z)
X =
Z
Z,)
ooPz,j v Z,)
ilJz,j
or
sCP
or C'
=
Pz,k
U =
1,Z; k
=
2,1)
X =
0
ooPz,j 2
P
z , j
Thus, we generate the representation fred = 2 2 2 0 0 0, which may be reduced,
by inspection, to L g + L ~ . An analytical method has been given in the
literaturel"'.
The linear combinations of the p, orbitals that we have used and which are shown
pictorially in Figure G.ld may be written as
pc, = pzJ + Pz.2
pcU = pzJ  Pz.2
(6.36)
(6.37)
The coefficients of unity follow from (6.24), and we shall defer normalization of
these functions until the next section.
Sec. 6.2] Setting UI) LCAO approximations 139
We need to consider next the px and pyorbitals. In relation to the z axis, they are
orientated as indicated by Figure 6.le, and may engage in 1t bonding by means of a
sidebyside overlap. Figure 6.3 shows the Px orbitals of the two oxygen atoms in
superposition along the internuclear axis c." so that this axis is normal to the plane
of the diagram; the py orbitals lie along the direction py but, for clarity, are not
shown.
The operation C'P moves Px into a direction that is taken, for convenience, to lie in
the cry plane shown in the diagram. We apply the equations in Example 5.2 (Section
p'
x
Fig.6.3 Two px orbitals in superposition along the direction of the internuclear axis: for
convenience, the trace of the cry plane has been used as the limit of the rotation for the
operation C'.
crpp .
= P . cos(rp)
+ Py,j
sin(rp) (j = 1, 2) ,
X,j X,j
Crpp .
= P . sin(rp)
+ Py,j
cos(rp) (j = 1, 2) .
Y,j y,j
They lead to a matrix with trace X= 4 cos(cp):
cos(rp) sin(rp) 0 0
sin(rp) cos(rp) 0 0
0 0 cos(rp) sin(rp)
0 0 sin(rp) cos(rp)
For the operation cr
v
, we can see from Figure 6.2 that Px is reflected across the cry
plane to p ~ so that the total angular change is 2 ~ , by the optical lever law. Hence,
cryPx,j = Px,j cos Ize l + "r.! sin(2rp) (j = 1,2),
crp .
y X,j
= (j 1, 2),
140 GroUI) theory and chemical bonding [Ch.6
cos(Zrp)
sin(Zrp)
0 0
sin(2rp)
cos(2rp)
0 0
0
0 cos(2rp) sin(2rp)
0
0 sin(2rp) cos(2rp)
so that the corresponding matrix, shown above, has a trace of zero. The operations i,
S'P and C generate matrices also of zero trace, so that the representation becomes
fred = 4 0 0 0 0, which may be reduced to n
g
+ Il.,
The linear combinations of p, orbitals that we have used and which are shown
pictorially in Figure 6.1e may be written as
pn, = Px.l + px.2
p7tg == Px.l  Px.2
(6.38)
(6.39)
It is not difficult to show that the 2s orbitals on the two oxygen atoms form a
representation that reduces to L + + L:, with linear combinations formulated
g
similarly to (6.36)(6.37).
6.2.4 Bonding and antibonding molecular orbitals and notation
We write (6.36)(6.37) or (6.38)(6.39) generally in the form
= N (c I/J + C .1. )
+ 1 1 2¥'2 '
= N(cl/J ct/J),
 1 1 2 2
(6.40)
(6.41)
where and \/12 are normalized atomic orbitals in the fractional amounts CI and
C2, and N+ and N are normalizing constants for the molecular orbitals. From the
discussion in the previous section, we have two o molecular orbitals of energies
I:
+
=
=
a + (3,
1+$
a  (3,
r=s
(6.42)
(6.43)
where L is the energy of the bonding molecular orbital formed from (6.36) or
(6.38), and is the energy of the corresponding antibonding orbital; S is implicitly
S12. Since we have defined (X as the energy of an electron occupying its own orbital,
it follows that the bonding orbital is lower in energy than this value by an amount 13,
whereas the antibonding orbital is higher in energy by the same amount. Exact
calculations show that the energy equivalences that we have just postulated are not
exact, but the differences may be neglected for our purposes.
Building up molecular orbitals
The energies of atomic orbitals for elements up to atomic number 20 follow the
order
Is < 2s < 2p < 3s < 3p < 4s < 3d .
Sec. 6.3] Ilelectron approximations 141
Molecular orbitals also are built up by the Aujbau principle, starting with those of
lowest energy.
We have treated the Is electrons of each oxygen atom as a 'core' that does not, to
a first approximation, enter into the bonding. Thus, we can write the electron
configuration for the molecular orbitals of oxygen in the following manner:
0:
2
The notation so, often called just c, implies a o bond formed by the overlap of s
atomic orbitals: likewise po implies a o bond involving overlap with a p atomic
orbital; in place of the core we could write (lcri (lcr
u
)2. The sequence represents
also the order of molecular orbital energies that apply to fluorine, but for diatomic
molecules up to and including nitrogen, the 2p7t
u
level lies below the 2pcr
g
.
Figure 6.4 is a qualitative molecularorbital energylevel diagram for the oxygen
"
,
,
"
( :'>
2s <, /" 2s
, ./
" "
, . ./
'il"
2 ocr
•
to
o ATOM
·CORE·
(1 sO" ) 2 (lso )2
• u
o MOLECULE
2
t.
o ATOM
Fig.6.4 Molecularorbital energylevel diagram for the oxygen molecule. The 'core' may be
regarded as the filled molecular orbitals (I sood(1soo" 2) or, in an alternative notation,
clooicloof The symbols 2:+, Il., L'i are used with molecules of symmetry CoO, or DoOh; for
more than one energy level of a given symmetry, numerical prefixes are added, as in 12:; ,
22:; and so on. The character table shows also the symmetry spanned by the AOs.
142 Group theory and chemical bonding [Ch.6
molecule. An antibonding orbital may be indicated either by the superscript asterisk
or by the appropriate subscript: however, the "g' and 'u' subscripts can be used only
with centrosymmetric species, such as a homonuclear diatomic molecule. The p1t
g
level is degenerate: the two orbitals are occupied singly, and the presence of
unpaired electrons accounts for the paramagnetic properties of molecular oxygen.
The po, and energetically higher levels are not occupied in the ground state.
Molecular orbitals may be denoted by lower case letters that correspond to the
upper case letters used for the irreducible representations'P! However, in the case of
the linear groups C
rov
and D"'h the alternative notation given in their character
tables, and in Figure 6.4, is in general use.
Total bond order
We can define a total bond order parameter K by the equation
K=(nn')/2 (6.44)
where nand n' are the numbers of electrons in bonding and antibonding orbitals,
respectively. Thus, for the oxygen molecule we obtain K = 2, which corresponds to a
classical double bond. In the case of nitrogen, we have
N:
2
2 2 4 2 0 a
(Core) (250" ) (250" ) (Zpn ) (2pO" ) (2p1l ) (2pO" ) ,
g u u g g u
and K = 3, a classical triple bond.
6.3 llELECTRON APPROXIMAnONS
The valence electrons of a molecule may be divided into a electrons and 1t electrons.
The a electrons are, to a satisfactory first approximation, localized in a bonds,
whereas the 1t electrons are delocalized to varying extents over the molecule. Many
chemical reactions can be explained in terms of 1t electrons, and it is possible to
treat them separately from the a electrons.
We considered a bonding in the carbonate ion in Section 5.6.2, where we
generated a representation for the a bonding:
3
3 C ~
I
E
3
D
3h
1:=
fa
which reduced to A ~ + E': we left the determination of the 1t bonding SALCs as an
exercise to the reader.
Following the rules for forming a representation, and using the outofplane pz
orbitals of oxygen, we write I', as
D3h I E 2C3 3C ~ all 283
r, 3 0 I 3 0
which reduces to A; + E". We now apply the projection operator technique to find
the SALCs for 1t bonding in the carbonate ion. From the character table for D
3h
,
taking the symmetry operations separately, we have
Sec. 6.3] Ilelectron approximations
143
E C
C
1
C'
C' C' , , cr S
S1
o cry
,
"
3 3 2 2'
2 h 3 3 v
cry
A" 1 1 1 1 1 1 1 1 1 1 1 1
2
E' ,
2
1 1 0 0 0 2 1 1 0 0 0
Using \111 as a generating function, we construct
PA' ,
=
1/1
1
+ 1/1 + 1/1 + 1/1 + 1/1 + 1/1 + 1/1 + 1/1 + 1/1
2 3 1 3 2 1 2 3
+ 1/1 + 1/1 + 1/1 = 4(1/1 + 1/1 + 1/1 ).
1 3 2 1 2 3
P
E"
= 21/1  1/1  1/1  2(1/1 )  1/1  1/1
1 2 3 1 2 3
= 2(21/1  1/1  1/1 ).
1 2 3
We need to construct a second function to complete the degenerate E"
representation. Following the arguments in Section 5.6.2 we obtain 3(\1'2  \1'3), and
when the derived functions for 7t bonding are normalized, we may write the 7t
SALCs, with an obvious notation, as
Ill' = (1/v3) ( 1l
+ 1l + 1l ),
,
a
1 2 3
1
= {
(1/v6) (21l
 1l  1l )
Ill' , ,
1 2 3 '
e
(1/v2) (1l
 1l J.
2 3
6.3.1 Using the Ruckel melecularnrhital method
The Huckel molecularorbital method is a further stage of approximation in the
solution of the wave equation. It has had particular application to 7t bonding in
organic conjugated molecules. and enables symmetry considerations to be used with
advantage. It should be noted that the symmetry arguments themselves are fully
valid, and that the Huckel procedure, notwithstanding it makes many
approximations, leads to useful results. This usefulness is bound up with the fact
that the molecular orbitals are determined by the symmetry of the system: no
information on the values of the parameters (X, and that occur in the eigenenergies
is needed. The orbitals may be then arranged in order of energy according to the
number and nature of the nodes that they possess.
The Huckel method assumes that each carbon atom of the molecule contributes
the Zp, atomic orbital and one electron to its 7t bonding system. Then the following
two simplifying assumptions are made:
Overlap integrals are set equal to unity or zero:
sij = 1 (1 = .JJ} (6.45)
.
Although values of Su are typically in the region of 0.2. this approximation does not
alter the relative positions of the molecular energy levels.
The Coulomb integrals for carbon atoms are accorded one and the same value:
Hi, = (X (6.46)
144 Group theory and chemical bonding [Ch.6
and the resonance integral is set equal to a parameter ~ for pairs of carbon atoms
that are adjacent, but zero otherwise:
H ..
1)
=
(3ij
=
{
(i and j adjacent),
(otherwise).
(6.47)
We recall that both ex. and ~ ~ are negative quantities. From (6.6)(6.7), the ith
normalized 7t molecular orbital is
4J
n
i
,
so that
N ~ f 4Jn,i4Jn,i dT
=
= N. \ c . .l/J.,
1 L. 1) )
)
N ~ 'f (\ c .. l/J . ) 2
d T
1 L. 1) )
)
= 1.
(6.48)
(6.49)
Expanding (6.49) for termsj and k, whcrej« k, we obtain
\ c ~ . f l/J.l/J. dT + \ L ~ c .. C'
k
I l/J·l/Jk dT = l I N ~ . (6.50)
L
j
1) )) L
j
k 1) 1) 1
':t:k
Using (6.45), the second term in me lennand side is zero, so that the normalization
constant is given by
N.
1
=
(6.51)
lfthe n terms in an LCAO molecular orbital are, for example, <j>j = 3\jf]  2\jf2 + \jf3,
then N = 114; when all e'i are unity. N = In.
Benzene
We consider the application of the Huckel method to benzene, first without using
symmetry arguments. The molecular structure of benzene is well known: each of the
6 carbon atoms contributes one electron in a pz orbital that is directed normally to
the molecular plane,
Following (6.45)(6.47), the secular determinant (6.35), concisely written as IH
y

E,. SyI, within the Huckel approximation becomes
ex.  £"
~
0 0 0
~ 1
~ ex.  IE." ~ 1
0 0 0
0
~
ex  IE.
n ~ ~
0 0
O.
(6.52)
0 0
~ ~ ex  IE." ~ ~ 0
0 0 0
~ 1 ex.  IE.
n ~
0 0 0 0
~ ~ ex.  £"
We make the convenient substitutiony 0= (ex  £,,)/[:\, leading to
Sec. 6.3] nelcctron approximations 145
(6.53) O. =
y 1 000 1
1 Y 1 000
o 1 y 1 0 0
o 0 1 Y 1 0
000 1 Y 1
1 000 1 Y
Expanding the determinant (see Section 2.5.3) leads to
l 6/ + 9/ 4 = 0 (6.54)
which must be solved for six roots before we can proceed further. This process can
be lengthy, and it is not immediately obvious that, in this particular case, the
expression can be factorized. It may be argued that, since programs exist for the
expansion of a determinant and the solution of a polynomial, solving (6.54) presents
little problem. However, if the determinant is large and time is costed, it becomes
important to show how the introduction of symmetry simplifies the situation.
Benzene has the point group D
6h
, and we can use the six 2pz outofplane atomic
orbitals to form a representation. In Figure 6.5a, these orbitals are normal to the
plane of the ring, with their positive lobes all directed upwards (or downwards). We
note that the symmetry axes C
6
, C
3
and C
2
are collinear: we let C ~ pass through
opposite carbon atoms, with C; bisecting opposite CC bonds; o, contains C ~ and
C
6
, and ad contains C; and C
6
.
Following rule 1 in Section 5.6.2, we generate f,,:
D
6 h
E 2C 2C C 3C' 3C
' 1
i 25 25 ah 3ad 3a
v
63222 36
r
7[
6 o o o 2 o o o o 6 o 2
Examination of the character table for D
6h
(see Appendix 11) shows that this
representation may be reduced to B
2g
+ E
1g
+ A
2u
+ E
2u
. The program RD6H that
carries out the reduction of a representation in D
6h
(see Appendix 12) may be used
here.
We showed in Section 5.6.2, demonstrating rule 2, that SALCs could be derived
by using the pure rotation group related to the molecular point group, C
6
in the case
of benzene; we could use D
6
instead, if we wished to avoid the appearance of
complex characters. The character table for C
6
is given below.
E C C C C
2
C
5
C
6
6 3 2 3 6
A 1 1 1 1 1 1
B 1 1 1 1
1 1
E
t
{
• •
1 e c 1 c e
• •
1 e c 1 c e
E
2
{
• •
1 c c 1 c c
•
•
1 c c 1 c c
146 Group theory and chemical bonding [Ch.6
Interms of this point group, the representation derived becomes:
which reduces to A + B + E\ + £2; these irreducible representations in C
6
correspond
to the first four columns, when written out fully, of the irreducible representations
B
2g
, A
2u
, E
l g
and E
2u
in D
6h
, since 8 0= exp(i27t/6) and 8 + 8* = 1.
Using the projection operator on II'I for carbon atom 1, we can write down by
inspection Pa.'t'l for all operations R under each irreducible representation a.
spanned by r ~ . We consider PBII'I as an example. In extenso, using (5.64), we have
P
B
I/11 = {OWE + (UO
C6
+ (UO
C3
+ (UO
C2
+ O W c ~
+ (UO
c
: } 1/1
1
= 1/1
1
 1/1
2
+ 1/1
3
 1/1
4
+ 1/1
5
 1/16' (6.55)
Following this procedure with all irreducible representations, we obtain a set of six
equations:
(6.56)
1/1 
5
1/1 +
5
•
£1/1 + e 1/1
5 6
•
£1/1  £ 1/1
5 6
•
£ 1/1 
5
1/1 +
4
 1/1 
4
.1. + ,I. +
'1'3 '1'4
£1/1 + 1/1
3 4
•
£1/1  1/1  £ 1/1 +
345
1/1 +
2
1/1 +
2
•
£1/1  £ 1/1
2 3
•
£1/1  £ 1/1 + 1/1 
234
1/1 +
1
•
= 1/1
1
 E tP
2

= 1/1 
1
= 1/1 
1
= 1/1 +
1
A:
B:
P
E
1
P
E
1 '
P
E
2
P
E
2'
As in Section 5.6.2, the complex coefficients can be eliminated by taking sums and
differences, like (PEl + PEl') and (P
E2
 P
E2
.)/i, giving the following normalized
SALCs:
.(6.57)
1/1
4
+ 1/1
5
+ 1/16)
1/1
4
+ 1/1
5
 1/16)
21/1 4  1/1 5 + 1/1 6)
1/1 6)
~ '
2
A (A ):
2u
B (B ):
2g
~ '
E (E ): { 3
1 19 ~ ' =
4
Sec. 6.3] Ilelectron approximations 147
The functions (6.57) are now used to form a new set of 1t molecular orbitals
according to (6.48); thus,
where the ci) terms obey the normalization condition
(6.58)
L
1
2
C ••
. 1)
)
= 1. (6.59)
The secular determinant is defined as before, except that in the Hij terms, the SALe
molecular orbitals of (6.57) are used. Hence, H
44
, for example, is given by
H
44
=
=
+ 21/1 H 1/1 + 21/1 H 1/1 + 21/1 H 1/1
203 205 206
=
=
a + (3. (6.60)
Similar results may be obtained for the other Hi) terms, but now all Hij (i '1=}) terms
are zero: any integral f<1>; 1110 <1>j d. with i not equal to} vanishes, because i and}
refer to different irreducible representations, or symmetries (see Section 5.5).
The secular determinant is now of the form
a+2(3E' 0
n
o a2(3E
n
o
o
o
o
o
o
o
o
= 0
o 0 0 0 0 a2(3 ~
We divide throughout by ~ and let y = (a.  £ x ) l ~ as before, giving a blockfactored
matrix that can be solved by inspection [the factors are the roots of (6.54)]; each
IY
+ 2 0 0 0 0 0
0
Y
 2 0 0 0 0
0 0 Y + 1 0 0 0
0 0 0 Y + 1 0 0
0 0 0 0 Y  1 0
0 0 0 0 0 Y 
11
= o. (6.61)
blockfactor is equal to zero, so that we obtain y = ±2, ±l, ±l, and Ex = a. + 2 ~ ,
a. + ~ (twice), a.  ~ (twice) and a.  2 ~ ; the a. ± ~ energies are degenerate; a. + 2 ~ is
lbl
148
GrOUI) theory and chemical bonding
(al
(e) (d) (e)
A : ex. +
2f3 E : ex. +
e E ex. + e
2u 19 19
@
@)
6 2
5 3
5 3
4
4
+ 
+
( fl (g)
(h)
E : ex.  e E : ex.
f3
B : ex.  2f3
2u 2u 2g
rcs.s
Fig. 6.5 Benzene: (a) CC and CH (j bonds form a regular, plane hexagon, with the Zp, AOs
of each carbon atom directed normally to the molecular plane. (b) 'Double streamer' 11: MO
of lowest energy, equivalent to (c) below. (c)(h) The lowest six MOs of benzene, with the
nodal planes indicated in (d)(h).
Sec. 6.3] Ilelectron approximations 149
the lowest (most negative) energy. The blockfactored matrix in this example is
particularly simple because it is diagonal in its entirety. It is for this reason that the
n molecular orbitals <1>"., are the same as the SALes <1>' "j: C;j = By for benzene.
Figures 6.5be illustrate six molecular orbitals for benzene. The electrons are fed
into the molecular orbitals according to the Aujbau principle (as with atomic
orbitals). Thus, the occupied molecular orbitals are az
u
of energy a. + and the
doubly degenerate elgof energy a. + each. The ground state configuration may be
written as (azu)z(elgt The unoccupied molecular obitals are those of energies a. 
(doubly degenerate) and a. 
A molecularorbital energylevel diagram is shown in Figure 6.6. If we compare
E" in benzene with that for three molecules of ethene (for which E" = a. + per
electron), we find that benzene is more stable by the amount
2(a. + + 4(a.  3[2(a. + =
This energy is the delocalization energy D" for benzene; since is approximately
75 kJ mol", D" is 150 kJ mol' in benzene.
The molecular orbitals of energies a. ± are the frontier molecular orbitals: the
highest occupied molecular orbital (HOMO) is elg and the lowest unoccupied
molecular orbital (LUMO) is ez
u:
frontier orbitals are important to the spectroscopic
properties and chemical reactivities of molecules, particularly unsaturated species.
6.3.2 Further features of the Hiickel molecularorbital theory
Under this heading we consider how the Huckel theory that we have developed so
far can be used to define the bond order, free valence and charge density parameters.
IlBnnd order
Formal double bonds do not exist in the Huckel approximation: each electron
contributes to the bonding, and the relative 1t bondings between pairs of adjacent
atoms are related to the coefficients c''/ by the itbond order Pi» sometimes called
the mobile bond order:
p. . = \' Tl
k
c. k C • k'
1,) L
k
1,),
(6.62)
where 11k is the number of electrons in the k1hoccupied 1t molecular orbital, i in Cj,k
refers to atom i in molecular orbital k. and j in Cj.k refers to atom j in the same
orbital; the sum is taken over all k occupied molecular orbitals.
150 GrOUI) theory and chemical honding
b
2q
icn.s
e
2u
I
I
/
I
I
/ /.'=======
..
I ./
I ./
<>
== v <,
,,,,
\ "" e
\ <, lq
\
\
\
\ 4
2u
IX  2fJ
IX  fJ
IX + fJ
IX + 2fJ
CARBON AOs C HMOs
6 6
Fig. 6.6 Molecularorbital energylevel diagram for benzene; the molecular orbital in Figs.
6.5bc is that of energy (a + and the degenerate molecular orbitals in Fig. 6.5dg are
those of energy (a ± 13); (t)(h) are unoccupied in the ground state.
Bond order is an important parameter, as it correlates well with bond length. If we
assume a bond order of unity for a (J bond, the total bond order ?iJ becomes (l +
Pij), a quantity that is comparable with the parameter K in (6.44). Figure 6.7
illustrates the graph of bond length against nbond order p, based on the standard
values of bond lengths given below. The graph can be drawn and interpolated by
hand or by the program [NT? (see Appendix 12).
p Bond length/nm
0 0.1542
2/3 0.1395
1 0.1337
2 0.1118
Sec. 6.3]
Bond length/lUI
0.1550 
0.1450 
0.1400 
0.1350 
0.1300 
0.1250 
0.1200 
Ilelectron approximations 151
O. 1. 1.5 .0
'IfBond order
Fig.6.7 Correlation between nbond order and bond length.
Free valence
We can measure the degree to which the ith atom is bonded to its neighbours by the
freevalence parameter Fj , defined by
F
1
, = M,  v r . k'
1 L
k
1,
(6.63)
where M, is the maximum bonding power of the ith atom (see Problem 6.6), and the
sum is over k occupied orbitals: for a carbon atom Me == 4.732. The value of the free
valence parameter is large when bonding is not strong, and it has a significant
bearing on chemical reactivity. Generally, the stronger the 1t bonding at atom i,
relative to other atoms in the molecule, the lower is the value of Fj , and the lower
the tendency to accept an attacking reagent. For example, position I in naphthalene
has a free valence of 0.86. with the next largest value 0.49: it is well known that
mononitration of naphthalene takes place at the lposition. Other indices of
reactivity have been proposed!" I.
152 Group theory and chemical bonding [eh.6
Charge distribution
If a carbon atom forms three CJ bonds and is 7t bonded, it will remain neutral as long
as there is an average of one electron in each 7t orbital. The charge distribution qi
may be taken as a deviation from neutrality, and is given by
=
1 \" 2
 L. "« c. k'
k 1,
(6.64)
where the symbols have the meanings as before. It is left as an exercise for the
reader to show that, in benzene, PiJ = 0.667, F
i
= 0.399 and qi = O. In pyridine (see
Section 6.3.4), position 3 has the largest negative charge among the ring carbon
atoms, and it is at this position that the nitronium ion NO; attacks in nitration.
6.3.3 Alternant and nonalternant hydrocarbons
Benzene is an example of an alternant hydrocarbon. An alternant hydrocarbon is a
planar, conjugated species in which the atoms can be divided into two sets, starred
atoms and unstarred atoms, such that no two starred or unstarred atoms are
adjacent. The starred atoms can be divided further into even and odd groups, such
that the starred and unstarred atoms in a molecule of an even hydrocarbon can be
interchanged to give an equivalent structure; some examples are shown below. In
even, alternant hydrocarbons the numbers of starred and unstarred positions are
usually equal; then the roots of the secular determinant fall into pairs y = ±a, ±b,
and so on, as we found for benzene. We will obtain a little more practice with the
Hiickel molecularorbital method by studying an example of an altemant
(methylenecyclobutene) and a nonalternant (methylenecyclopropene) hydrocarbon.
ALTERHANT
:0:
Benzene (even)
HOHALTERHAHT
3
Kethylenecyclopropene
6
5 2
4 3
5 2
4 3
Kethylenecyclobutene (odd) Fulvene
Sec. 6.3] Ilelectron approximations 153
o
Methylenecyclobutene
The secular determinant (6.35) for this altemant hydrocarbon is of size 5 x 5. The
principles of its solution remain the same as before, and the eigenenergies Ej (i =
15) in increasing order are:
a + < a + < <x < a  < a 
As indicated above, it is a feature of even, altemant hydrocarbons that their energies
are disposed symmetrically about = o. The eigenvectors ci; are listed below, in the
order of i given above; the reader may wish to continue the study of this molecule by
calculating the bond order, free valence and charge parameters.
i 1 2 3 4 5
j 1 0.26096 0.65719 0.00000 0.65719 0.26096
2 0.55735 0.43516 0.00000 0.43516 0.55735
3 0.46471 0.18452 0.70711 0.18452 0.46471
4 0.43516 0.55735 0.00000 0.55735 0.43516
5 0.46471 0.18452 0.70711 0.18452 0.46471
Methylenecyclopropene
As an example of a nonalternant hydrocarbon we consider methylenecyclopropene,
point group C
2v.
We may write the secular determinant from an inspection of the
structural formula: y [= (a  Ex occupies each position on the main diagonal; a
'1' appears in the position corresponding to an atom adjacent to that represented by
y in any row; thus, atom I is adjacent to atom 2, but atom 2 is adjacent to atoms 1, 3
and 4, and so on:
y 1 0 0
1 Y 1 1
o 1 y 1
o 1 1 Y
However, we shall work this example in full: the character table for C
2v
has been
given in Section 4.2, and will be found also in Appendix II.
We take the twofold axis along the C
1C2
bond, cry as the vertical plane through
the C
1C2
bond, and rr as the molecular plane. With this data and using the outof
plane pzorbitals on the carbon atoms we generate the representation
E C
2
cry cry'
4 2 2 4
which can be reduced toA
2
+ 3B
1
.
Next we construct a table that shows how the wavefunctions for the atoms respond
to the symmetry operations, and includes the characters of the A
2
and B
1
irreducible
representations The entries are of the form OR\jf:
154 Group theory and chemical bonding [Ch.6
CZy
E C
cry
.
2
cry
"\
1/1
1
1/1 1/1
1
1/1
1 1
1/1
2
1/1
2
1/1
1/1
2
1/1
2 2
1/1
3
1/1
3
1/1
1/1
4
1/1
4 3
1/1
4
1/1
4
1/1 1/1
3
1/1
3 4
A 1 1 1 1
2
B 1 1 1
1
1
The A
z
representation is antisymmetric across the cry plane, which relates atoms 3
and 4, so we expect the atomic wavefunctions \j/3 and \j!4 to form the symmetry
adapted orbital \j/3  '1'4. The HI representation is symmetric across the cry plane, so
that the same functions will combine to give '1'3 + '1'4 . Atoms I and 2 are unique,
unrelated by symmetry to any other atom in the molecule, so that their symmetry
orbitals will be \j/1 and ip, respectively. We can confirm (or deduce) these findings
by using the projection operator (5.68) as follows (see also Section 5.6.2):
PA 1/1
1
= P
A
1/1
2
= 0,
2 2
P
A
1/1
3
= 1/1
3
 1/1
4
(= P 1/1' we need only one of them),
A 4'
2 2
P
B
1/1
1
=
1/1i '
1
P
B
1/1
2
=
1/12'
1
P
B
1/1
3
1/1 + 1/1
4
(=
P
B
1/14;
we need only one of them) .
3
1 1
Thus, we obtain the normalized, symmetryadapted LCAOs:
~ ' = (1/"'2)(1/1  1/1 ),
1 3 4
~ ' = .10
2 '1'1'
~ ' = .1.
3 '1'2'
~ 4 ' = (1/"'2) (1/1 + 1/1 J.
3 4
Next, we set up the secular determinant (6.35), just as in the example of benzene.
We give three examples of the H
u
terms:
H = (1/2)J (1/1  1/1 )H (1/1  1/1 )
11 3 4 0 3 4
H =
(11"'2) J1/1 ,R 1/1
d. = (3,
32 2 0 1
H =
(1/"'2) J1/1 R' (1/1
+ 1/1 ) d.
43 2 0 3 4
d. = lX.  (3,
"'2(3.
Sec. 6.3] Ilelectron approximations 155
The corresponding terms of the secular determinant are a.  ~  £i, ~ and . . . f 2 ~ ,
respectively, which we replace, in order, withy  I, 1, and n. The secular equations
(6.34) are, concisely,
where
\' ,2 =
L
k
C
k i
l.
The determinant from (6.65) becomes
I y 
1 0 0 0
0 y 1 0
0 1
Y
';2
0 0 ';2 y + 1
== 0,
0,
(6.65)
(6.66)
(6.67)
and the two factors can be solved for y. The 1 x I block is the A
z
representation, and
gives y = I. The 3 x 3 block corresponds to the three B
1
representations: solving the
determinantal equations gives y = 2.1701, 0.31111, 1.4812
We come now to the coefficients c ~ i ; evidently, the coefficient associated with the
I x 1 matrix is unity. Expanding (6.65), we have for y = 2.1701
= 0,
(6.68)
where M is the matrix of the 3 x 3 block in (6.67). Taking each of the values of yin
turn and following either one of the procedures given in Appendix 9, we find
C = 0.28185 C = 0.61164
c = 0.13924 }
22 23 24
C = 0.81522 C = 0.25362 c
34
=0.52066 . (6.69)
32 33
C = 0.50594 C =0.74939 C = 0.42713
42 43 44
We can now write the true molecular orbitals for each irreducible representation by
combining these coefficients with the SALes:
A: <I> =  0.7071/1 + 0.7071/1
2 1l,1 3 4
B: <I> = 0.2821/1 + 0.6121/1 + 0.5231/1 + 0.5231/1
1 1l,2 1 2 3 4
. (6.70)
B
1
, : <I> = 0.8151/1 + 0.2541/1  0.3681/1  0.3681/1
1l,3 1 2 3 4
B " :
<I> = 0.5061/1  0.7491/1 + 0.3021/1 + 0.3021/1
1 1l,4 1 2 3 4
Using (6.62)(6.64) we can determine the bond orders, free valences and charges for
this species; the results are tabulated below, together with bond lengths interpolated
156
Group theory and chemical bonding
[Ch.6
from Figure 6.7. We see that, within rounding errors, the charges sum to the
expected zero, and the cr
v
symmetry, relating atoms 3 and 4 is evident in the results.
Atom pair nBond order Bond length/ntn Atom Free valence Charge
1 2 0.758 0.138 1 0.974 0.488
2 3 0.453 0.143 2 0.068 0.123
3 4 0.818 0.137 3 0.462 0.182
4 2 0.453 0.143 4 0.462 0.182
It is possible to calculate the dipole moment fl of this species. From the diagram for
this molecule shown above, we choose atom C
2
as a convenient origin, and resolve
the other bond moments along the direction of the C\C
2
bond:
fl= {2[O.182 x 0.143 x 10,9 x cos(300)] + (0.188 x 10'9 x O.135)}e
= 1.78 x 10'29 C m, or 5.30,
since 1 0 (Oebye unit) = 3.3356 x 10,30 C m. This value is probably too large: the
higher approximation selfconsistent field theory indicates a dipole moment of 1.2
D. The disparity arises because the Huckel treatment concentrates the charge at the
atoms, whereas it is distributed over the whole molecule. Furthermore, the
calculation does not include o electrons, which may make a significant contribution
to the dipole moment. An elementary calculation shows the effect of charge
distribution on dipole moment:
.__.__.__.__. .__.__.__.__.
0.1 0.1
+0.2
.1 .1
o
.1
0.2
.1
+0.1 +0.1
.1 .1
o
.1 .1
(a)
(b)
In (a), the dipole moment is O.08e; in (b), a simple distribution of the same total
charge reduces the dipole moment by 25% to O.06e.
Ruckel's 4n + 2 rule
This generalization relates to the relative stabilities of cyclic, conjugated
hydrocarbons of formulae C
n
H, . If the total number of 1t electrons is N, then we
express this number in terms of a smaller integer p, with the following results.
N = 4p + 2 Molecule is stable: benzene (p = 1);
N =4p + I Molecule forms a radical: cyclopentadienyl (p = I)
N = 4p Molecule is unstable: cyclobutadiene (p = 1)
Huckel calculations for the pentadienyl system as a cation, radical and anion show
the effect of four, five and six 1t electrons on the energy IE.,.:
C H+ C H· C H
55 55 55
T[ Electrons
E,' IB
T[
4
5.2
5
5.9
6
6.5
Sec. 6.3) Ilelectron approximations 157
(6.71)
6.3.4 Working with heteroatoms in the Hiickel approximation
The Huckel method can be used with molecules containing heteroatoms by
modifying the Hi; integrals in the secular determinant; the 0. and 13 parameters are
changed to 0.' and W, as follows:
a' = a + h (3
c xcx'
=
=
(6.72)
where Table 6.1 lists the literature[22
j
values of h, and k; .
Pyridine
We shall illustrate the procedure with reference to pyridine CsHsN; the ring is
numbered clockwise, starting from nitrogen. The molecule is aromatic, and each pz
orbital provides one electron. The reference axes are positioned as shown in the
diagram; x lies normal to both y and z. The symmetry element C
2
lies along z, cry is
the xz plane and c ~ the yz (molecular) plane. A representation is obtained from the
outofplane Zp, orbitals, as with benzene:
l' Z
, 1
N
6 c/: ""c 2
I ····:·········1··7 y
c : C
5 ""c/ 3
4
6 2
C
2
2 6
E
r c,.J, _
~
which reduces to 24
2
+ 4B
1
• We lise the same procedure as with
methylenecyclopropene, but we present the results here more concisely.
158 Group theory and chemical bonding [Ch.6
Table 6.1 Some parameters for the Huckel theory
Atom h k
Carbon h = a k = 0.9
C CC
h = a k = 1.0
C co
aram
h = a k = 1.1
c c=o
Nitrogen h = 0.5 k 0.8
N CN
h .. = 1.5 k = 1.0
N C=N
Oxygen h· = 1.0 k = 0.8
0 c=o
h .. = 2.0 k = 1.0
0 c=o
From the projection operator technique, we obtain:
+ = a (= P
A
2
P
A
+ 0<
2
= + 0<
\115 and \116 behave like tV2 and \113, respectively. Next we use P
B I
with tVI to \114; \Ill
and \114 do not couple with other atoms under C2v:
PH
=
+ +
+
0<
1
1
PH
=
+ + +
0<
+ ,
6 6 6
1
PH
=
+ + +
0<
+ •
5 5 3 5
1
PH
=
+ + +
0<
4 4 4 4
1
We now normalize the SALCs that we have formed:
<1>' = (11"'2)  )
1 2 6
<1>' = (1/"'2)  )
2 3 5
<1>' =
3
(6.73)
<1>' (1/"'2 + )
4 2 6
<1>' = (1/"'2) + )
5 3 5
<1>' =
6
Sec. 6.3]
Ilelectron approximations
159
The secular determinant is constructed from the appropriate Hij terms, using the
principles already discussed, and the appropriate data from Table 6.1; we must not
lose sight of the fact that <1> refers here to the nitrogen atom, labelled 1 in the
diagram:
H
ll
=H
22
= H
44
= H
s s
= H
66
= a; H
33
= a +
H\2 =H
2\
H
34
=H
43
=
H
45
=H
s 4
H
S6
= H
65
=
All other Hi] terms are zero, and we now construct the determinant:
O'.,E (3 0 0 0 0
(3 O'.
E
0 0 0 0
0 0 0'.+0.5(3 E 0.8(3v'2 0 0
o. =
a a 0.8(3v'2 O'.·E (3 a
0 a a (3 (3 E
(3v'2
a a a a (3v'2 0'. f.
Making the usual substitution, Y = (a  we find
y 1 0 a a a
1 y a a a a
a a y + 0.5 0.8\"2 a a
= o.
0 a 0.8v'2 y 1 a
a a a 1 y v'2
a a a a v'2 y
The blockfactoring is again not as complete as in the example of benzene.
Nevertheless, we have achieved considerable simplification. The 2 x 2 determinant
relates to the A
2
irreducible representation and, by inspection, y = ±1 so that two
values for E. are a ±
The 4 x 4 determinant relates to the B
2
irreducible representation; it is a little
more complex, but we can solve it as before. However, we may make use of the
symmetric nature of this Huckel matrix to solve it by Jacobi diagonalization; this
procedure is contained in the program EIGN (see Appendix 12). The fourth order
determinant is set in the form
160
Group theory and chemical bonding
0.5 0.811'2 0 0
0.811'2 0 1 0
0, =
0 1 0 11'2
0 0 11'2 0
[eh.6
(6.74)
that is, y is put equal to zero: the program adds the values of 1. The eigenvalues and
eigenvectors are listed in Table 6.2, from which we can determine the true 1t
molecular orbitals, using (6.58) and (6.59), with c:I>/ formed from the results in
Table 6.2. We give an example from the B
I
representation, E = a. +
= + + +
1£,1 3 4 5 6
= + + )111'2 + + )111'2
1 2 6 3 5
+ O.
4
= + + +
+ O. + O. .
5 6
Table 6.3 lists the coefficients of the complete set of six 1t wavefunctions in
ascending order of energy. We are now in a position to calculate the bonds orders,
freevalence parameters and charges. We give an example of each, and list the full
results in Table 6.4.
From (6.62), with} = 13, we have
PI,2 = 2 x 0.4242
2
x 0.3856 + 2 x 0.6653
2
x 0.2336 + 2 x 0 x (1/2)
= 0.638.
From (6.63), and considering the nitrogen atom, we have
f
N
= 2 + ...}3  (2 + 0.638 + 0.638) = 0.456
From (6.64), again considering nitrogen, we find
qN = 1  (2 X 0.4242
2
+ 2 X 0.6653
2
) =0.245
Table 6.2
Eigenvalues and eigenvectors from determinant (6.74)
i 1 2 3 4
Eigenvalue,
E
1.9543 1.0618 0.6673 1. 8488
i
Eigenvectors,
c'. 0'
0.4242 0.6653 0.5642 0.2431
1)
0.5453 0.3304 0.5821 0.5046
0.5857 0.4020 0.2499 0.6580
0.4239 0.5354 0.5295 0.5033
Sec. 6.3] Ilelectron approximations 161
Table 6.3 Complete wavefunctions for pyridine
i 7 1 2 3 4 5 6
IR B B A B A B
1 1 2 1 2 1
E
i
1.9543 1.0618 1.0000 0.6673 1. 0000 1. 8488
c ..
1)
0.4242 0.6653 0 0.5642 0 0.2431
j 1 0.3856 0.2336 1/2 0.4116 1/2 0.3568
0.4142 0.2842 1/2 0.1767 1/2 0.4653
0.4239 0.5354 0 0.5295 0 0.5033
0.4142 0.2842 1/2 0.1767 1/2 0.4653
0.3856 0.2336 1/2 0.4116 1/2 0.3568
Table 6.4 Bond orders, free valences and charges for pyridine
Atoml Bond order, p .. Free valence, '!f. Charge,
qi
I,) 1
1, 2' 1, 6 0.638 ,
2, 3' 5, 6 0.687 ,
3, 4' 4, 5 0.655 ,
1 0.456 0.245
2, 6 0.408 0.094
3, 5 0.390 0.005
4 0.421 0.067
Figure 6.8 illustrates a molecularorbital energylevel diagram for the pyridine
molecule, and Table 6.5 shows the agreement between the experimental bond
lengths and those interpolated from Figure 6.7. For this species E" = 6a. +
and D", against two molecules of ethene and one of the species HN=CH
z
, is
this value corresponds to a resonance energy of approximately 110 kJ mol", less
than in benzene, and in accord with experiment.
162
GrOUI) theory ami chemical bonding [Ch.6
The dipole moment of pyridine calculated from the charges qi in Table 6.4,
assuming an average bond length of 0.14 nm, is 4.27 D. The experimental value is
2.21 D, and the larger calculated value is typical of results from Hiickel molecular
orbital calculations, which often lead to values in excess of both experimental values
and those obtained through calculations made at a higher level of approximation.
Table 6.5 Interpolated and experimental bond lengths for pyridine
Atom pair
1,2; 1,6
2,3;5,6
3,4;4,5
Bond length/nm (intp)
0.139(7)
0.138(7)
0.139(4)
Bond length/nm (expt)
0.134(0)
0.139(5)
0.139(4)
/4b
I 1
/
/
/ /2a
/ 2
I /
/ / ./ ...... 3b
1
~
I / " " "
~ . /
,/
\\
,
\ \ "
\ \ ,
\ \ "j1
\ \ la
2
\ \2bj1
\ 1
\i1
lb
1
(X  1. 849(3
(X  (3
(X  0.667(3
(X + ~
(X + 1. 062(3
(X + 1. 954(3
CARBON AOs C H NMOs
5 5
Fig. 6.8 Molecularorbital energylevel diagram for pyridine; different molecular levels of
the same symmetry are distinguished by a numerical prefix, taking the lowest energy level of
each type as 1. The electronic configuration for the molecule may be written as (l b,)2 (2bd
(lad; the frontier orbitals, HOMO and LUMO, are l a, and 3b
1
, respectively.
Sec. 6.3] Ileleetron approximations 163
6.3.5 More general applications of the LeAO approximation
In this section, we discuss briefly sigma bonding in the two species
pentafluoroantimonate ion and methane.
o 2 o o
E
4
Pentafluoroantimonate(III) ion
We consider first the inorganic pentafluoroantimonate(III) ion [SbFsf, point group
C
4v
; Figure 6.9 is a stereoview of the species. We set up axes with z along the axial
SbF bond, and x and y along the equatorial SbF bonds; o, is the plane xz and O"d
the vertical plane bisecting the x and y axes. We can make use of the diagram in
Example 5.5. in studying this molecule.
We will generate a representation for 0" bonding, using the p orbitals of the
fluorine atoms that all have their positive lobes pointing towards the antimony atom.
It is evident from Figure 6.9 that the axial bond is unique, so that the corresponding
orbital, pz, is also unique and spans the totally symmetric irreducible representation
AI.
The movements of the equatorial p orbitals under the symmetry operations of C
4v
lead to the representation
which reduces to Al + B
I
+ E. We now apply the projection operator technique to
the wavefunctions \IIj (j = 14), with \III and \113 along ±x, and \112 and \114 along ±y.
The changes in \III and \1'2 under the symmetry operations are tabulated below.
Fig. 6.9 Stereoview of the pentatluoroantimonate ion, [SbFsf: z is along the axial SbF
bond, x and y along equatorial SbF bonds, cry the plane xz, crd the vertical plane at 45° to x
andy.
E C C
3
C
O'v O"v O"d O"d
4 4 2
1/1
2
1/1
4
1/1
3
1/1
1
1/1
3
1/1
2
1/1
4
1/1
3
1/1
1
1/1
4
1/1
4
1/1
2
1/1
1
1/1
3
164 GrOUJl theory and chemical bonding [eh.6
Applying the projection operator, we find:
PA 1/1
1
=
(1/11
+ 1/1 +
1/1 + 1/14) •
2
3
1
 1/14)'
P
B
1/1
1
=
(1/11
1/1 + 1/1
3
2
1
P
E
1/1
2
=
(1/11
 1/1 ).
3
We need a second function for the E representation. In discussing this problem for
the carbonate ion (see Section 5.6.2), we defined a generating function in a direction
that was orthogonal to the first chosen function. Such a direction in this example is
that of the y axis, or of the wavefunction \112 The above tabulation shows how the
symmetry operations act on \112, and applying P
E
to it we find
PE \112 = (\112  \114)
which is a satisfactory second function for the E representation. We write the
normalized SALes as follows:
A:
<1>' =
(l/2) (1/1 + 1/1 + 1/1 + 1/1 I,
1
1 1 2 3 4
B:
<1>' =
(l/2) (1/1  1/1 + 1/1  1/1 )
1
2 1 2 3
4 •
{
<1>' = (1/v2) (1/1  1/1 )
3 1
3 •
E:
<1>' = (1/v2) (1/1  1/1 ).
4 2 4
The orbitals for antimony can be derived in a similar manner. The sand pz orbitals
transform separately as AI, whereas Px and p, transform together as E. There will be
some interaction between the sand pz orbitals of the component species to form
combined orbitals of the type ( 1 / ~ 2 ) ( s ± p.). However, the nodal plane of the
antimony pz orbital coincides with the equatorial plane of atoms, so that such
interaction would be limited to the s orbital of antimony.
Reference to the character table for C
4v
shows that B] is spanned by the d
x
2.
y
2
orbital. This function could interact only with that of B
1
in fluorine. It seems
unlikely that the relative energies would permit this combination to any significant
degree; a molecularorbital energylevel diagram is shown in Figure 6.10.
Sec. 6.3]
(4p)
(4s)
Ilelectron approximations
Ib
1
i

1
 ,
Ja \
_1_
i
_
l
\
/'7 .J,,, \
.  ~ / , ,
\
(2p)
165
ANTIMONY ATOM
2
(SbF) ION
5
FLUORINE ATOMS
Fig. 6.10 Molecularorbital energylevel diagramfor a bondingin the pental1uoroantimonate
ion.
A first look at methane
Methane belongs to point group T
d
, and its character table (see Appendix 11) shows
that the Px, py and pz orbitals span the irreducible representation T
2
; the s orbital
spans the fully symmetric AI. We can generate a representation of Td by examining
the effect of the symmetry operations on the four bonds from carbon to the Is
orbitals of the hydrogen atoms. It may be found helpful to construct models to assist
in the perception of the symmetry operations of Td and their relation to those of the
cube.
EXAMPLE 6.1. Draw an equilateral trangle of side, say, 60 mm on a thin card, and on each
of its sides maw an identical triangle. Cut out the drawing, score the edges of the first
triangle, fold the outer triangles inwards and secure; mark the comers 14. In a similar
manner, construct four squares on the sides of a square, of side 6 0 1 ~ 2 mm. Fold to form five
faces of a cube and secure. Fit the tetrahedron into the cube such that an edge of the
tetrahedron forms the diagonal of the 'missing' face of the cube. Now, the symmetry
elements commonto both polyhedracoincide.
To obtain the desired representation for the a bonding in methane, it is convenient
to detail the action of the symmetry operations on the CH bond vectors. With the
tetrahedral model from Example 6.1, it is straightforward to obtain the following
results:
Leaves all vectorsunmoved
Leaves one vector unmoved
Moves all vectors
Moves all vectors
Leaves two vectors unmoved
XE = 4;
x
C3
=I;
X
C2
=0;
X
C3
= 0;
Xad =2.
166 GrOUl) theory and chemical honding [Ch.6
2 o
Thus, we generate the representation
Td ___"_
fred 4
We denote the hydrogen Is orbitals by s, (i = 14): the action of the symmetry
operators on Sl are summarized as:
E s.; 8C
3
2(Sl + S2 + S3 + S4); 3C
2
S2 + S3 + S4;
68
4
2(S2 + S3 + S4); 6ad 3s
1
+ S2 + S3 + S4·
The projection operator leads to the first SALC: 6(sj + S2 + S3 + S4), or
normalized, <D; = (l/2)(sj + S2 + S3 + S4). A formal derivation of the SALCs that
span the T
2
representation is more complex. However, we can deduce them by
inspection, ensuring that they match in phase the orbitals on the central, carbon
atom. Figure 6.11 shows a tetrahedron set in a cube as described in Example 6.1,
and the interaction with pz is illustrated. There are two s orbitals that interact with
pz (+) and two that interact with pz (). Thus, we have the combination (s,  S2  S3 +
S4): if we apply the same argument to the Px and py orbitals on the central atom, we
can complete the derivation of the four orthonormal SALCs:
=
(1/2) (5 + 5 + 5
+ 5 )
1
1 2 3 4
=
(1/2) (5  5  5
+ 5 )
2
1 2 3 4
= (1/2) (51
 5 + 5  5
)
3
2 3 4
(1/2) (5 + 5  5
 5 )
4
1 2 3 4
+
"
" \
" \
, ,\
\
\
"
"
"
/
/
I
I
I
I
I
I
I
I
I
S
J
Fig. 6.11 Diagrammatic representation tor the SALes formed between hydrogen 1sand
carbon 2pz AOs, spanning T
2
in methane.
Sec. 6.4]
Schemes for hybridization
167
It is clear from the geometry of p orbitals that, without some qualification, the use of
these four SALCs will not lead to the four identical bonds that are required in
methane. The sand p orbitals of carbon are all involved, but they are combined in a
way that leads to a structural equivalence, and this requirement brings with it the
opportunity to discuss hybridization.
6.4 SCHEMES FOR HYBRIDIZATION: WATER AND METHANE
We have discussed chemical species where bonding with pure sand p orbitals does
not lead to the molecular geometry that has been determined experimentally.
Furthermore, the molecularorbital theory involves delocalization of the electrons
over a molecular orbital and, if several atoms are so involved, the idea of these
electrons forming specific bonds becomes somewhat vague.
Hybridization is a concept, something that we have devised, that assists in the
visualization of chemical bonding. It channels electrons into bonding directions, and
so restores the bond as an overlap of directional orbitals, hybrid orbitals, that are
combinations of the orbitals that we have described so far. We shall discuss
hybridization first in relation to water and methane.
r
P
z
Fig. 6.12 Orthogonality and the formation of hybrid orbitals, using p orbitals as an example.
Consider the orthonormal py and pz orbitals as vectors along the corresponding
axes. Let another p orbital, denoted by Pu make an angle +8/2 with the z axis, Figure
6.12. Then, we have
Pu = pzcos(8/2) + Py sin(812) (6.75)
An equivalent orbital pv directed at an angle 8/2 to the z axis is then given by
Pv = p, cos(8/2)  py sin(8/2) (6.76)
While py and pz are orthonormal, Pu and pvwill not be necessarily so, unless we
choose the correct value for 8. Applying the orthogonality integral, we have
I
p p dT = I {[p cos(8/2) + p sin(8/2)] [p cos(8/2)
u v z y z
 p sin(8/2)]} dT
y
2
I
2
sin
2(8/2)
I p ~
= cos (8/2)
pz
dT dT
2
sin
2(8/2)
cos (e). (6.77)
=
cos (8/2)
=
168 Group theory and chemical bonding [eh.6
This integral vanishes only for 8 = 90°, as we would expect for the orthogonal p
orbitals.
Hybridization implies a contribution from two or more orbitals, so we may write
two hybrids in the form
h
h'
= C S + C P
s p u
C S + C P
s p V
}.
(6.78)
where c, and c
p
measure the contributions of the pure sand p orbitals to the hybrids.
An alternative, common notation for (6.78) h, = P ± A.S, where ~ . 2 = e: Ie ~ .
By applying now the orthonormality criteria (6.78), we have
= J(c s + C P )2 dT
s P U
2 2
= C + C =
s p
1: (6.79)
the orbitals are orthonormal, and JSPII dt = 0; also
Jhh' dT =J(c s + c p )(c s  c p ) =
s pUs p V
+ c; J PuP
v
dT + csc
p
J (sp
u
+ sP
v
) dT
Hence, using (6.75H6.77),
c 2 + C 2 cos(8) 0
s p
and, since c . ~ + c ~ =1.
=
O. (6.80)
(6.81)
2
C
s
2
C
P
= cas(S)
cos In l  1
1
=
1  cas(S)
}
(6.82)
Table 6.6 lists some common values of 8 and the corresponding sand p character
for an sp' hybrid, where x = c ~ Ic: = 1/1...
2
. The terms c
2
and 1...
2
refer to electron
density contributions to the hybrid; c and A. refer to the wavefunctions themselves.
The water molecule has an H ~ O ~ H bond angle (8) of 104.4°: thus the p character
(e ~ ) is 0.801, as shown in Table 6.6. The orbital function could be written as
\1'(Sp4) = 0.446s + 0.895p, (6.83)
and a pair of them define the OH bond directions. The remaining sp electron
density is confined to another hybrid orbital orthogonal to both bonding hybrids. To
Sec. 6.4] Schemes 1'01' hyhridization 169
Table 6.6 Contributions of sand p to sp' hybrid orbitals
Orbital 8/deg c
2
c
2
').} (= c: Ie ~ )
s p
P
90 0 I 0
Sp4
104.4 1/5 4/5 1/4
Sp3
109.47 1/4 3/4 1/3
Sp2
120 1/3 2/3 1/2
sp 180 1/2 1/2 I
s I 0
preserve the C
2v
symmetry, its axis must bisect the HOH bond angle. Figure
6.13 illustrates some aspects of the discussion so far.
We have used part of the filled 2s orbital of oxygen in forming the hybrid orbital,
and energy is expended in this process. However, it is more than compensated by
the increased overlap with the hydrogen Is orbitals, compared with an overlap
between pure Px and py . The remaining oxygen 2s and 2p electron density,
equivalent to a pair of electrons, occupy another orthogonal hybrid orbital. Their
offcentre distribution, together with the 'Ione pair' Zp, electrons make a major
contribution to the polar nature of the water molecule. This view is supported by the
fact that the dipole moment of the water molecule is 1.8 D, whereas that of
difluorine monoxide F
2
0 is only 0.2 D: the stronger polarity of the FQ bond,
directed away from the lone pairs, reduces the effect of their contribution to the
dipole moment ofF
2
0 .
6.4.1 Symmetrical hyhrids
In general, the combination of n atomic orbitals leads to n hybrid orbitals, so that we
must consider now the third orbital for the water molecule, which lies in the
direction of pz.. We could write the third orbital in the form
h" = c', S + c p
s p'
(6.84)
Orthogonality with h and h' leads to the relationship c.c ~ + cpcp cos(8/2) = 0 and,
with c s 2 + C P 2 = L c ~ 2 = 0.398. so that we have
\/111 = 5'10.602 + p"",O.398.
However, the situation is more revealing if we write (6.78) fully:
(6.85)
h =
P
z
cos(S/Z)
+ P sin(S/Z) + As
}.
y
(6.86)
hi
=
P
z
cos(S/Z)
 P sin(S/Z) + As
y
where ').} = c; Ic ~ = cos(8). Since we know that 8 is 104.4°, we have
h 0.613p + 0.790p + 0.499s
}
z y
(6.87)
hi
= 0.613p 0.790p + 0.499s
z y
170
Group theory and chemical bonding
[eh.6
xaxis
Is
yaxis
(a)
o +C<Jo() Ibl
p
s
xaxis
yaxis
p + A,S
(el
Fig.6.13 Hybridization schemes for water. (a) Bonding through two H(ls) and O(2px,2py)
would lead to a bond angle 01'90
0
and a small overlap. (b) Formation of a hybrid orbital, with
the internuclear axis coincident with the axis ofthe p orbital. (c) Bonding between two H(ls)
and O(p + A.s) hybrid orbitals leads to a bond angle of 104.4
0
and strong overlap. The two
hybrid orbitals are almost mutually independent: if hydrogen atom HI is replaced by CH, to
form CH,OH, the bond length OH is almost unchanged, thus providing a basis for the
observed characteristic bond lengths and energies.
These hybrids are normalized by the constant N, where
N = 1/[(0.613)2 + (0.790)2 + (0.499)2]1/2 = 0.895
so that we obtain the orthnormal functions
h = 0.549p + 0.707p + 0.4465
}
Z
Y
(6.88)
hi
= 0.549p  0.707p + 0.4465
Z
Y
We should note that (0.707
2
+ 0.549
2)1/2
= 0.895, as in (6.83), where the p functions
were treated jointly. The third hybrid h" may now be written as
h" = c.s + cypy + c, Pz. (6.89)
Sec. 6.4]
Schemes for hybridization 171
The three coefficients can be evaluated through orthonormality and the fact that the
squares of the contributions of a given orbital over n hybrids must sum to unity.
Thus, we have
(6.90)
so that c, = ±0.776. We make the (arbitrary) choice that c, = 0.776. We can deduce
that c
y
is zero, because (6.88) shows that the py orbital is used fully in forming h
and h': C ~ = 2(0.707
2
) = 0.9997. (Actually, '0.707' is precisely "212.) It follows
now that C
z
= ±0.63 1.
Ifwe apply the orthogonality criterion to h (or hi) and h", we obtain
J
hh
" dT  (0 549p + 0 707p + 0.446s)
 . z . y
x (±0.631p + 0.776s) dT = 0,
z
whereupon it is clear that the negative sign must be taken for the coefficient of pz in
h" in order to achieve normalization.
The two lone pairs are now the Zp, and hybrid h" orbitals: an alternative model
would be hybrids that are their linear combinations:
~ ' =
11
~ ' =
11
(l/v2) (p
x
+ hi I)}.
(l/v2) (p  hi ')
X
(6.91)
The models are equivalent, and Figure 6.14 is a molecularorbital energylevel
diagram for water in the first of them. We can summarize the position that we have
reached for the water molecule in the tabulation below.
Bonding orbitals
Lonepair orbitals
%s character
0.20
0.60
%p character
0.80
0.40
172 Group theory and chemical bonding [Ch. G
2a
1
/
,
,
/
2b
,
2
/
/
<, ,
/ /
<,
,"
j /
...... "
j/
"\
?/
./; (Ls )
lb
/1
~      l i  l 
//
(2p)
'\,
//
,",,'
/
,,", lb
/ /
,2
i1
 / /
/
,
,
la
/
~ i  l  /
OXYGEN ATOM H 0 MOLECULE
2
HYDROGEN ATOMS
Fig. 6.14 Molecularorbital energylevel diagram for hybrid IT bonding in the water
molecule: the lonepair orbitals are shown as px and the hybrid O.776s  O.63Ipz; the core is
not included, but is sometimes labelled as la..
The four hybrid orbitals are directed very closely to a tetrahedral arrangement
around the oxygen atom. This picture is very similar to the qualitative model for the
water molecule proposed by Bernal: the molecule was treated as a tetrahedron, with
two charges of +Y2 and two of Y2 at the four apices. The positive apices
corresponded to the bonded hydrogen atoms and the negative apices to the
nonbonding electrons. This model can be useful in considering the role of the water
molecule in ice and in hydrates.
Walsh diagrams
The change in energy as a function of the bond angle for the occupied molecular
orbitals in hydrides of the type AH
2
may be plotted between the extremes of 0° and
180°, Figure 6.15; such a diagram is termed a Walsh (correlation) diagraml"'. A
change in shape of the molecule that increases the overlap of atomic orbitals will
lower the energy level of the corresponding molecular orbital. It is noteworthy that
molecular orbitals of different symmetry have their maximum bonding effect
(minimum binding energy) at differing values of the HAHbond angle.
For the water molecule an energy compromise is attained at a bond angle value of
104.4°. At an angle of 180°, the states 2a, and Ib
2
in an AH
2
dihydride become
degenerate, as in the linear beryllium hydride BeH
2
, where bonding leads to the
energy levels Ia, and Ib
2
(Can you demonstrate these levels for BeH
2
?). At the other
extreme of 0° the levels Ib, and Ib
2
become degenerate, and the species is then a
linear diatomic molecule, like oxygen or hydrogen fluoride.
Sec.6.4J
Schemes for hybridization 173
Energy/relative
scale
Ib
2
I
I
o
:/ 104.4
I
I
o
HAH bond
angle/deg
Fig. 6.15 Walsh diagram for AH
2
type dihydrides; the dashed line shows the position for the
H
20
molecule.
Further study of methane
The electronic configuration of carbon is (lsi (2S)2 (2px)1 (2pi, and in order to
form four bonds the 2s and 2p electrons must be used. Since the bonds are to be
equivalent, hybridization is invoked. Let each hybrid be of the form
h = P + AS. (6.92)
Then, if each HCH angle is to have the tetrahedral value of 109.47°, Table 6.6
shows that A= 1/3 and the hybrid is denoted Sp3. Figure 6.16 shows the orientations
of the hybrids in relation to a cube. If we think of the central, carbon atom as an
origin of coordinates, then the hybrids can be regarded as vector combinations of the
px, py and pz orbitals. The hybrids have been labelled according to these
combinations; thus, the hybrid labelled I, I, I may be interpreted as the
combinations of unit vectors, such as
ip, + jpy + kp;
Hence, we can write the four SALCs as
A:
~ I
I I
{
~ I
2
T:
~ I
2 3
~ I
4
=
=
=
(1/2) (s
+ PI
+ P
2
+ P ),
3
(1/2)(s
 PI
 P
2
+ P ),
3
(1/2) (s
+ PI
 P
2
 P )
3 '
(1/2) (s
 PI
+ P
2
 P
3
).
174 Group theory and chemical bonding [eh.6
A more formal deduction of these hybrids is given in Appendix 10.
(1,1,1)
Jv
x
(1,1,1)
(1,1,1 )
Fig. 6.16 Hybrid Sp3 orbitals in methane, showing their directional relationship to the cube.
The carbon atom is at the centre of the cube, and the relative coordinates of the comers of the
cube that lie on the orbital axes (the C
3
axes of the cube) are shown. Thus, 1,1, I may be
regarded as the vector ip, + jpy + kp;
6.5 PHOTOELECTRON SPECTROSCOPY
It is reasonable to enquire at this stage about any experimental evidence that
supports the molecularorbital schemes that have been drawn up. The technique of
photoelectron spectroscopy allows an identification of individual orbital energy
levels, by measuring the ionization energies of molecules as electrons are expelled
from different orbitals under the influence of an exciting radiation.
Monochromatic radiation is allowed to impinge on to a gaseous sample species,
and the ejected electrons are analysed and recorded in order of their kinetic energy.
Since energy is conserved under ionization, we have an equation reminiscent of the
photoelectric effect, except that there are now several levels of ionization to be
considered:
(6.93)
where Y2I1l
e
V
2
is the kinetic energy of the emitted electron, and If is the ionization
energy for the orbital <D
i
. The kinetic energy is measured by an electrostatic analyser
which spreads the emitted electrons according to their energy. The results are
recorded as a plot of electron flux, that is, electrons emitted per unit time, against
energy. Since the exciting frequency v is known, the energy Ii can be determined.
Sec. 6.4] Schemes for hybridization 175
Electron
flux
Fig 6.17 Diagrammatic photoelectron spectra of the hydrogen atom and hydrogen molecule.
The single sharp band for the hydrogen atom occurs at 13.6 eV, which is the ionization
potential for the hydrogen atom: H 411 + e'. TIle hydrogen molecule ionizes at 15.5 eV: H2
4 H ~ + e'. The peaks forming the broad band arise through vibrational modes of the
hydrogen moleculeion.
Figure 6.17 is a bargraph representation of the photoelectron spectra of atomic and
molecular hydrogen. Normally, this technique produces only the singlyionized
species of a molecule M:
(6.94)
(6.95)
This ionization energy is approximately the negative of the orbital energy for one
electron species, and the values obtained experimentally are in accord with results
that we have determined qualitatively:
. E
H
< E < E
H+ H
2 2
A theorem by Koopman states that this relationship remains true for multielectron
species provided
(a) that the orbitals in /1;( are sensibly unchanged from those in the molecule M
itself, and
(b) that electron correlation remains the same in both the M and u+ species.
In fact, the two approximations have opposing effects on the orbital energy, so
that the energy of ionization measured by photoelectron spectroscopy is a good
approximation to true ionization energy.
The fine structure (see also Section 6.7.1 )present in the band for the hydrogen
molecule arises from the vibrations of its nuclei. Molecules in their ground state are
normally in their lowest vibrational state, that is, V = 0, where V is the vibrational
quantum number (q.v.). When an ion is formed under excitation, the species will
exist in higher states (V = I, 2, ...). Then, not all of the irradiating energy will be
converted into kinetic energy of the emitted electrons:
1 2
hv = m v + I . + C
2 e J vt b '
176
Group theory and chemical bonding [Ch.6
where Evib is a vibrational energy in the excited state. Thus, according to the energy
level occupied Evib can vary, leading to the fine structure lines. If the bond lengths of
the molecule and its ion are similar the fine structure is minimal, whereas if they are
disparate the newlyformed ion will be in a geometry very different from its
equilibrium condition, and fine structure will be clearly evident.
Before concluding this brief treatment of photoeloectron spectroscopy, we
consider the diatomic species oxygen and nitrogen which we have discussed earlier
in this chapter; Figure 6.18 shows the spectra for these two molecular species. Other
ionizations that are not shown occur at the approximate values, for N
2
(2scr)g 34 eV,
for O
2
(Zso), 26 eV, and for O
2
(2scr)g 40 eV.
The first ionization energy of oxygen is less than that for nitrogen because the
(2pn)i electrons are antibonding. There are also two bands for the oxygen (2pcr)g
ionization: the singly ionized oxygen molecule has three unpaired electrons, (2pcr)g,
(2Px1t)g and (2p
y1t)g.
They can be all a. (or all ~ ) spins, or two a. and one ~ (or a. and
two ~ ) : these two electronic states will have different energies arising from electron
correlation interactions, so that two bands appear for the (2p1t)g ionization. A similar
effect occurs for the (2pn)u ionization, and examination of oxygen under greater
resolution shows that the band at approximately 17 eV is split. The order of
ionization energies that we discussed earlier is confirmed, and Table 6.7 lists some
properties of elements up to neon.
Electron
flux
(2plll
./ 9
Oxygen, 02
(2pO'"l
9
,/ (2pcT)
,/ 9
Nitrogen, N
(2pO'l
2
'\,g
(2pll)
u
,/
( 290'"l
u
12 14 16 18 20 22 24 E/eV
Fig. 6.19 Photoelectron spectrum for molecular oxygen and nitrogen: the reversal of
the order of the energies for the (Zpo), and (2pcr)g molecular orbitals is indicated.
Sec. 6.5] Photoelectron spectroscopy
177
Table 6.7 Hydrogen to neon: orbital ionization energies of atoms, and bond lengths
and dissociation energies of moleules; the data in parentheses are true ionization
energies.
ATOMS MOLECULES
!leV dlnm DJeV
Is 2s 2p
H 13.6 (13.60) H
2
0.041 4.48
He 24.6 (24.56)
H+
0.16 2.65
2
Li 5.4 (5.39) He; 0.18 2.39
Be 9.3 (9.31) Li
2
0.27 1.14
B 14.0 (15.15) 8.3 (8.29) B
2
0.19 2.84
C 19.4 (24.37) 10.6 (11.26) C
2
0.14 6.24
N 25.6 (29.59) 13.2 (14.54) N
2
0.10 9.76
0 32.3 (35.13) 15.8 (12.02)
N+
0.12 0.75
2
F 40.2 (34.97) 18.6 (17.42) O
2
0.11 5.12
Ne 48.5 (41.06) 21.6 (21.55)
0+
0.12 6.48
2
F
2
0.12 1.60
Electron
flux
It
2
o 10 20 30 40 E/eV
Fig. 6.19 Photoelectron spectrum of methane: the JahnTeller effect causes a splitting of the
degeneracy of the lt2level. One member of the triplet at 10 eV is unresolved in this diagram.
The ionization of the la, molecular orbital occurs at 290 eV.
Figure 6.19 shows the photoelectron spectrum for methane. The bonding molecular
orbitals are (2so/ and (2Sp30 ) 6, corresponding to the symmetries of the 2al and It
2
levels, respectively; the lower energy (lso)2 molecular orbital may be looked upon
as forming the 1a1 level. The molecular ion CH; has 5 electrons, and the It
2
level
is degenerate. There are three ways in which these electrons can be arranged among
three energy levels. The JahnTeller theorem states that a degenerate, nonlinear
species possesses an instability that leads to a distortion of its symmetry and thus
178 Group theory and chemical bonding [Ch.6
splits the degeneracy. It follows that the ionization of the degenerate molecular
orbital should correspond with three closely similar but not identical values.
The spectrum confirms this result, although the third peak of the 1t2 level is
overlapped at the resolution under which these experimental results were obtained.
The ionization of the la, level occurs at approximately 290 eV, so it is not shown on
the diagram.
Sulfur hexafluoride
As a final example here, we consider the molecule of sulfur hexafluoride SF
6
, a very
stable species ;0 = 991 kJ mol") that is chemically rather unreactive. We will
find that a model is helpful in visualizing the symmetry operations on this molecule,
as we did with methane.
EXAMPLE 6.2. If you have a ballandspoke kit available, insert spokes into a ball so as to
form the orthogonal ±X, ±y and ±Z axes. Alternatively, a ball of plasticine and six cocktail
sticks can be used. Number the x, y and z axes I, 3 and 5, respectively, and let x, yand z
be numbered 2, 4 and 6. (Figure 6.36, see later, has been set in this orientation.) It will now
be possible to visualize any or all of the 48 symmetry operations of the octahedron.
Sulfur hexafluoride belongs to point group 0h. If we compare the character tables of
0h and 0, we see that they are related by the direct product
o e c, = Oh. (6.96)
zaxis zaxis zaxis
. ....,
xaxrs
r.
yaxis yaxis
71:;;::'
zaxls
I /
... ' ..; yaxis
71
xaxis
zaxis
../
/
yaxis
//
xaxis
d 2 2
x v
Fig. 6.20 d Atomic orbitals illustrated by surfaces of constant 1",1
2
in their conventional
setting on the x, y and z axes. The lobes of d
z
2 lie along the z axis, and those of d
x
2.y 2 are
along x and y. The lobes of d
zx
, dyz and d
xy
lie in the corresponding planes. The shading
indicates how the corresponding", functions change phase: light +, dark . The axes may be
changed by cyclic permutation: thus, if x, y and z are permuted to z, x and y respectively, dz2
is renamed d
x
2, d
x
2_
y
2 becomes dy2 _z2and so on.
Sec. 6.5] Photoelectron spectroscopy 179
Thus, from our earlier discussions, we anticipate (correctly) that we can obtain
SALCs for sulfur hexafluoride by working with the simpler point group O.
We can form a representation by considering the action of the symmetry operators
on a set of six p atomic orbitals lying along the SF bonds, with their positive ends
all pointing towards the sulfur atom. Thus, by the usual rules, we find
o
6C'
2
2
6C
4
o
8C
3
E
6
::J=
which reduces to A1 + E + T
1
: A 1 is totally symmetric, and is spanned by s orbitals
(x
2
+ l + i refers to a sphere); E is doublydegenerate and is spanned by the
product functions 2z
2
 x
2
l (equivalent to 3/  r
2
) , or the d
z
2 orbitals, and by x
2

l, the d
x
2_
y
2 orbitals; both of these functions are of even parity. The triply
degenerate T
1
is spanned by the triplet x, y and z which corresponds to the
anti symmetric p orbitals. It is evident now that in Oh the corresponding
representations are A
I g
+ E
g
+ Ts.: Figure 6.20 illustrates I\VI
2
for the d orbitals; the
shaded regions correspond to the negative phase for the \jl functions.
In working with so many symmetry operators we need to be very systematic. We
choose to work the C
3
operations from the four positive quadrants of an octahedron,
starting with C
3a
in the +x, +y, +z quadrant and proceeding anticlockwise around a
C
4
axis. The C ~ operations act as shown below:
acts between
C;a
x, y
C
2c
x, z
C
2d
X, z
The orientations of the other operators are clear from the notation.
The orbitals \j/" \j/3 and \1/5 are directed along the x, y and z axes respectively. The
action of each of the operators on these orbitals is shown by the tabulation below.
Next, we apply the projection operators for the AI, E and T, irreducible
representations and normalize the resulting SALCs.
o E C C C C C C C C C C C
3a 3a 3b 3b 3c 3c 3d 3d 2z 2y 2x
"'6 "'4 "'3
"'2 "'5 "'6
"'3 "'2 "'2
"'2 "'2 "'1
"'4 "'3 "'4
"'5 "'6 t/J
6
C
4
C
3
C
4z 4y
C
3
C
4y 4x
C'
2a
C'
2b
C'
2c
C' C' C'
2d 2e 2f
"'4 t/J
6
"'5 t/J
1
t/J
1
t/J
3
t/J
1
t/J
3
t/J
3
t/J
5
t/J
6
t/J
1
"'5 t/J
1
"'2 t/J
4
t/J
3
t/J
6
t/J
6
t/J
2
t/J
2
t/J
4
t/J
5
t/J
6
t/J
2
t/J
3
t/J
4
180 Group theory and chemical bonding [Ch.6
P
A
t/J
1
= (1Iv'6) (t/J + t/J + t/J + t/J + t/J + t/J );
1 2 3 456
1
~ ] applied to \j!3 and \I's give equivalent SALCs. With PT
l
, we have
=
=
=
(lIv'Z) (t/J  .1. )
1 'P2 '
( lIv'Z) (t/J _.J.)
3 'P4 '
(l/v'Z) (t/J  t/J I.
5 6
These three SALCs for T\ are orthonormal one to the other and to the first SALC
derived. For the E representation, we have
PE\l'l (l/..J12) (2\1
/]
+ 2\1'2  \jl]  \1'4  \j/S  \j/6),
P
E\j/3
(l/..J12) (\1/1  \1'2 + 2\/13 + 2\1'4  \j!s  \j!6),
PE\j!S (1/..J12)( \1'1  \1/2  \1/3  \1'4 + 2\j!s + 2\1'6)'
We note that we have derived three E functions where only two are needed.
Secondly, since they are all different they cannot all be correct. If we accept PE\j!I,
which is orthonormal to the first four SALCs derived, then P
E\j!3
and PE\j!s cannot
be used as such. We now have a problem similar to that which we encountered in
studying ammonia and the carbonate ion. We could treat the problem here in a
similar manner, but we choose to introduce two other treatments.
Let the second E function be expresed in the form
Then by applying the fuIl orthonormality criteria between this and the other five
functions, we can show readily that e =f= 0, a = c and b = d. Thus, we have a
function (or its negative)
Alternatively, consider the functions spanned by E; they are 2z
2
 x
2
 y2 and x
2

y2. The first of these functions is matched by P
E
\j/ l , and the second E function is
obtained from matching in phase x
Z
l (see Figure 6.20) which is achieved by the
combination (\j/] + \jIZ  \jf3  \1'4); we list the set of SALCs below in standard form.
The orbitals involved in the c bonding of sulfur to six fluorine atoms are, thus, s,
three p and two d orbitals. The hybrid combination of these orbital is usually known
as d
2
sp3, and is of particular significance in octahedral coordination, as we shall see.
Sec 6.6]
Cyclization and correlation
181
A (A i.
1
+ + + + +
=
V6
S
I Ig I 2 3 4 5
r
1
+ ) =
   +
d 2
E (E l :
2 3 4 5 6 Z
g
1
+  
d 2 =
2:
2
3 2 3 X y
1
 ) =
V2
P
x 4 2
(T :
1
 ) T =
V2
P
y I Iu 5 4
1
 ) =
V2
P
z 6 6
For convenience, we restate part of the character table for
E C
2
A 1 1 1 1
I
A 1 1 1 1
2
B 1 1 1 1
I
B
2
1 1 1 1
If we delete all reference to cr. then cr; must disappear too, and the character table
for C
2
remains. Alternatively, if we excise then one c operation is also lost, and
we are left with Cs
A molecularorbital energylevel diagram is shown in Figure 6.21. The bonding
molecular orbitals are relatively close in energy to the atomic orbitals of fluorine,
and the twelve bonding electrons occupy fully the alg, egand tl
u
molecular orbitals.
The large energy gap between e
g
and the nearest nonbonding molecular orbitals t2g
accounts for the chemical inertness of sulfur hexafluoride. We note also that the
orbital ionization potentials for the occupied orbitals are high, at approximately
39.3,41.0 and 44.1 eY.
182
Group theory and chemical bonding
t· \
,. I
I
====,1
• II
• I I
19 \ \
(E + T ) , I I
9' 2; l \ \ \
___ 29 \ II
, \\1
"d' \ \ ,\
I III
\ II,
(T,.> I \\\
I II
, \ \\\
(Jp) \, \ \\
\ \ I,I
(A
l
; ) \ \ \\\
___ \ \ III
(3.) \ \ \ \ \ ~
\ \ \ '(A + E + T l
\" t t ~ U
\ \ \ )
\ \ , ,;' ========
, \ \ / ' ~ ~ ".'
\ \ \ e ,.' /1
\ \ \ 9' / /I
\ \ I=H H=/ /,'
\ \ I'
\ \ I I
\ \ ttu / I
\ \ / I
\ ,":lL...t1:ll:/ I
\ =rr=rr=Tf= I
I ,
, I
\ a
t 9
"
'H'
[Ch.6
SULfUR ATO" SUlFUR HEXAFLUORIDE
sr6
FLUOR I NE ...TOM5
6 r
Fig.6.21 Molecularorbital energylevel diagram for cr bonding in SF6. The large energy gap
between e
g
and h
g
explains the low reactivity of SF6. This gap and its variation with ligand
type governs the chemistry of transitionmetal coordination compounds.
6.6 Cyclization and correlation
Many chemical reactions are governed by symmetry, a feature expressed by the
WoodwardHoffman rules[27] which we summarize: the ratedetermining step of a
reaction is a concerted process, that is, a reaction at one atom centre triggers
reaction throughout the molecule; secondly, at least one aspect of orbital symmetry
is preserved throughout the reaction. Thus, the orbitals must conform throughout
the reaction to this symmetry. If we can deduce whether or no the energy state of the
products is higher than that of the reactants, it will be possible to predict whether
the given reaction path is allowed or forbidden.
cisButal,3diene undergoes cyclization to form the one product cyclobutene in
two ways, thermally and photochemically. However, if the butadiene carries cis or
transdialkyl substituents, the thermal process leads to cisdialkylcyclobutenes
whereas the photochemical process produces transdialkylcyclobutenes. In order to
understand these reactions, we need first to consider how the symmetry changes in
the course of a cyclization.
Sec 6.6]
E
Cyclization and correlation
E
183
A
B
1
1
A'
A"
1
1
Thus, we havethe following correlations between the irreducible representations of ~ v and
its subgroups C
2
and C.
C
2v
~
C
2
or
C
s
A correlates with A or
AI
1
A correlates with A or
AI I
2
B correlates with B or
AI
1
B correlates with B or
AI I
2
and, whichever subgroup is employed, one of these two symmetries must be
preserved during the cyclization process.
In order for butal,3diene to cyclize, the terminal 7[ orbitals must rotate by 90° to
a position of potential overlap. The two 7[ orbitals could rotate in the same sense,
conrotatory, or in opposing senses, disrotatory. Reaction will take place at the
frontier molecular orbitals: the highest occupied molecular orbital (HOMO) in
butadiene is <1>2 (lbg) when the process is thermally induced, but the excited <1>3
(2a
u
) orbital is used in the photochemical process. Thus, we need to know the signs
of the 7[ wavefunctions at C, and C
4
in the two states represented by <1>2 and <1>3. In
Figure 6.22, we use a vertical bar I or I to represent an outofplane 7[ orbital at a
carbon atom, whereas +   or   + shows the same orbital after a 90° rotation;
the ± signs emphasize the phases of the orbitals. The study of several such reactions
shows that the thermal cyclization is conrotatory and the photochemical cyclization
disrotatory for n = 4m, where n is the number of 7[ electrons and m is an integer 0, I,
2, ... ; the opposite situations obtain for n = 4m + 2.
In order to study the conservation of orbital symmetry we need to consider
molecular orbitals other than the highest occupied. The orbital correlations follow
the scheme in Table 6.8, which may be derived with the aid of the character tables
given above.
Table 6.8 uses the same stick models for butadiene and cyclobutene: it lists the
molecular orbitals for butadiene and cyclobutene, and the symmetry states under C
2
(conrotation) and 0" (disrotation). From the data there, we can derive the correlation
diagrams between the energy states of butadiene and cyclobutene by making use of
the noncrossing rule, deriving from quantum mechanics, which states that the lines
linking energy states of identical symmetry designation never cross. The diagrams
for the two mechanisms are shown in Figures 6.236.24. On the one hand, if
the bonding molecular orbitals in butadiene correlate with the bonding molecular
1M Group theory and chemical bonding rcn.s
...... I I·····
/ ,
("l +
__ H _
2 2
t c l
1,
H +/ r,+/H
2 + + 2
(bl
__HL
H
+ + CH'\cH__
2 2
(dl
Fig. 6.22 Cyclization of butal ,3diene to cyclobutene. (a) The HOMO ¢2 in the ground
state, (la
u
)2(lbgf (b) The HOMO¢J in the excited state, (laui (lbg)1 (2an)l, of butadiene;
the signs at CI and C
4
should be noted. (c) Thermal cyclization to cyclobutene by a
conrotatory mechanism, preserving C2 symmetry; the 7t MOs at C
1
and C
4
in (a) have been
rotated clockwise by 90°. (d) Photochemical cyclization to cyclobutene by a disrotatory
mechanism, preserving rr symmetry; the 7t orbitals at C
1
and C4 in (b) have been rotated in
opposite senses by 90°. In each case, the rotated 7t orbitals forma (J bond between C
1
and C
4,
with transfer of the double bond to the 2,3 position.
Table 6.8 Orbital correlations in the cyclization of butadiene
BUTAl,3DIENE
+ + + +
j)kj
j/jkj j)kj j)kj
+ +
l%l l%l l%l
1 2 3 4
C b a b a
2
(J"
a'
a' ,
a'
a' ,
CYCLOBUTENE
+ + +
/
,
/!!"'" /!!"'"
/
,
  + +  
  +   +
• •
cr 1l 1l cr
C a b b a
2
(J" a'
a' ,
a'
a' ,
orbitals in cyclobutene, the thermal reaction is allowed. On the other hand, if the
correlation is between bonding and antibonding orbitals, the thermal reaction is
forbidden but the photochemical process can operate. If we examine the crossings
shown in Figure 6.24 for the disrotatory mode, for example, those between <1>2 in
Sec 6.6] Cyclization and correlation
]85
butadiene and the 1t' molecular orbital in cyclobutene, and between <1>3 in butadiene
and the 1t molecular orbital in cyclobutene, are permitted because one line belongs to
symmetry a" and the other to symmetry a'. However, the crossings that might have
been considered for <1>2 in butadiene to (j' in cyclobutene and for <1>4 in butadiene to
1t in cyclobutene, still in the disrotatory mode, would be forbidden, because both of
them involve the symmetry of a".
•
s<T
 a   __ ..:
t
3
b
 
•
pll
a
t
~ j  1  
a
t 
1j1b     .::: 
BUTAl,3DIENE
pll
 bj1
sCT
j1
a
CYCLOBUTENE
Fig 6.23 Molecular orbital correlation diagram for the cyclization of cisbutaI,3diene to
cyclobutene by the conrotatory (thermal) process. In this reaction, the correlation links the
ground state of butadiene to that of cyclobutene, (scr)2(pnf
•
s<T
 
a' ,
t
3
___ ,,7",
_ a
•
pll
.. .... 11j1
.. a
t ......
~ j  1  ,  , »>
a
pll
t
_l
j

1
 , __
a
BUTAl,3DIENE
a'
_ _ _ sCT
 a'j1
CYCLOBUTENE
Fig 6.24 Molecular orbital correlation diagram for the cyclization of cisbutal ,3diene to
cyclobutene by the disrotatory (photochemical) mechanism. In this process correlation exists
between an excited state of butadiene (<1>2) and an excited state of cyclobutene (pni, as well
as between the two ground states.
186 Group theory and chemical bonding [Ch.6
Now we can understand more clearly the photochemically induced cyclization. If we
postulate an excited state (<1>1)2 (<1>2)1 (<1>3)' arising from absorption of incident
radiation, conrotatory correlation would lead to the state (sa)' (pn)2 (so")', whereas
the disrotatory mode would form (sa)2 (pn)' (pn·)l. The disrotatory mechanism is
symmetry allowed here because it leads to a state of lower energy in cyclobutene. In
the substituted butadienes, the thermal reaction takes place by a conrotatory
mechanism but the disrotatory mechanism must be invoked for the photochemical
cyclization.
6.7 GROUP THEORY AND TRANSITIONMETAL COMPOUNDS
Transition metals are series of elements that are characterized by incomplete shells
of d or f electrons. We shall consider mainly the first transition series of elements,
scandium to copper, for which the dshell occupancy increases from (3d)1 to (3dt It
is from these electrons, and transitions involving them, that the transitionmetal
compounds derive their valence properties. and the optical, spectral and magnetic
characteristics associated with them.
The application of molecularorbital theory to transitionmetal compounds is
generally called ligandfield theory. As we would expect, it allows for the
delocalization of the electrons of the transition metal and those of the attached
species, or ligands. A typical transitionmetal compound is hexamminecobaIt(III)
chloride, [Co(NH3)61CI3 , illustrated diagrammatically in Figure 6.25.
A simpler and earlier approach that considers the interactions of a transition
metal ion with the electrostatic field of the surrounding ligands is known as crystal
field theory. This name arose from the consideration of the interaction of a sodium
ion Na+ with the electrostatic field of the surrounding ions in a crystal of sodium
chloride. We shall be able to gain a basic understanding of transitionmetal
compounds with this relatively simpler theory.
NH
3
,
" NH3
" \
" \
" \
" \
" \
NH
3
Fig.6.25 The octahedral complex ion [Co(NH
3
kf +: the x and y axes lie along the equatorial
NH,CoNH
3
directions.
//
/
/ /
/ /
/ /
/ /
/ /
  /
6.7.1 Electronic structure and term symhols
A study of the quantum mechanics of the hydrogen atom[16.
19
1 shows that a one
electron wavefunction may be written as
Sec 6.7] GrOUI) theory and transitionmetal compounds
187
\I' = R(r) Y(8, $) a." (6.97)
where R(r) is the radial function, Y(8, $) is a spherical harmonic, or angular
function, and as is a spin function that is independent of the spatial coordinates r, 8
and $. The function is specified by the four quantum numbers, n, I, m, and s.
The principal quantum number n takes integral values, starting from unity, and
determines the nature of R(r). The quantum number I is associated with the 6(8)
function ofthe spherical harmonic, and represents the orbital angular momentum of
the electron, and is quantized in units of [/(/ + 1)]
112
h. The values of I range from 0
to n  1, and these two quantum numbers give rise to the following notation for
atomic orbitals:
Orbital type
n 1
o
s
2
1
P
3
2
d
4
3
f
The motion of an electron gives rise to a magnetic dipole moment: the vector
representing this moment is perpendicular to the plane of orbital motion of the
electron and is the z reference axis; +z corresponds to an anticlockwise motion, as
would be viewed down +z towards the origin. The quantum number m, occurs in
both the 6($) and <1>($) functions of the spherical harmonic, and takes the integral
values I, 1 1, ... 0, ... I + 1, I, making 21+ 1 values in all.
"1 = 0
Fig. 6.26 Vector model for electron orbital angular momentum: a given value of mi is the
projection of any generator of the corresponding cone, including the circle (limiting cone of
semiangle 90°) on to the z axis; the x and y components of momentum are unspecified, in
accordance with the uncertainty principle.
It follows from the quantization through I that only certain orientations of the
magnetic moment vector are permitted, as shown by Figure 6.26. Thus, we have the
the following correspondences:
o
o
I
0,±1
2
0, ±1, ±2
3
0, ±1, ±2, ±3
In addition to the orbital angular momentum, the electron possesses an inherent
spin angular momentum, as though it were spinning on an axis passing through it.
The spin quantum number is symbolized by s, and its projection on the z axis by m..
188
Group theory and chemical bonding [Ch.6
The spin angular momentum is quantized in units of [s(s + I)J
I/2
1i, and the
component msli can, in principle, take the values s, s • 1, ... s + 1, s, or 2s + 1
values in all. However, a detailed analysis of spin shows that s has the single value
of 1;'2, so that there are only two (2s + 1) orientations for the spin vector. In one
orientation m, = 1;'2 (spin up, or u, or t), and in the other m, = Y2 (spin down, or ~ ,
or .J.).
We can form a vector sum of the orbital and spin angular momenta. If we assume
that space and spin quantization are independent, their sum) has the magnitude I ±
Y2, where) is a quantum number for the combined angular momenta. The
interaction between the orbital and spin momenta leads to the state) = I  Y2, when
the moments are antiparallel, being lower in energy than that with) = I + 1;'2, when
the moments are parallel. For other, intermediate states of the number), we make
use of the ClebschGordan series[28
I
: for two sources of angular momenta jl and j2,
the vector sum j = jl +h is satisfied by the series of terms
) =)1 +h, )1 +h  1, )1 +[:  2, ... , Iii hi
provided that j, and h together with anyone of the terms of the ClebschGordan
series can form a triangle. In our application j, and h have the magnitudes of the
quantum numbers I and s: their combination follows the same triangle rule, and we
obtain the following series
) = 1+s, 1+ s  1, 1+ s  2, ... , II  s\
EXAMPLE 6.3. We shall find the values of the total angular momentum for (a) an s electron
with spin, (b) a p electron with spin, and (c) a d electron with spin.
1
1
1
sl
1
j
1
(a) o· thus, the minimum value of  is
2'
and =  only. ,
2
1
1
1
s Imin
1
j
3 1
(b) 1,
2;
thus,  and 
2 2
1
1
1
s Imin
3
j
5 3
(c)
2,
2;
thus,  and 
2 2
RussellSaunders coupling
We consider next the situation with multielectron atoms, and specifically the case
where a partlyfilled shell exists over and above several closed shells: for example,
the cobalt ion in [CO(NH
3)6JCh
has the configuration (1S)2 (2S)2 (2p)6 (3S)2 (3p)6
(3d/, for which the K (n = 1) and L (n = 2) shells are closed, or filled, and the M (n
= 3) shell is partly filled. Although each electron has its unique set of four quantum
numbers, there is a significant interaction between the electrons that we shall
approximate by means of RussellSaunders, or LS, coupling.
The total orbital angular momentum of all electrons in a species is symbolized by
L, and similarly the total spin angular momentum is denoted by S. Letter (state)
symbols are assigned to the different values of L as follows, as with the scheme for
oneelectron atoms:
L
Symbol
o
S
1
P
2
o
3
F
4
G
5
H
6
I
Sec 6.7] GrOUI) theory anti transitionmetal compounds 189
If one electron has an orbital angular momentum quantum number I) and another
electron 1
2
, their combined orbital angular momentum is quantized in units of [L(L
+ 1)]1I2Ji and, from the ClebschGordan series, L takes the series of values
/) + /2, /1 + /2  I, II + /2  2, ..., I/[  /21
EXAMPLE 6.4. We find the total angular momentum and the state symbols for (a) two p
electrons, (b) two d electrons, (c) one p and one d electron, and (d) three p electrons.
(a) h =h = I; the minimum value of III  hi =0, and L =2, I, 0, with the state symbols D, P
and S;
(b) II =l: =2, III l2lmiJl =0; L =4,3,2, 1,0 (G, F, D, P, S);
(c) h =I, l: =2, III /21miJl =I; L =3,2, I (F, D, P);
(d) With more than two electrons we proceed pairwise. For two of the p electrons, h =h =1,
III  hi = 0; thus, for these two electrons, L' = 2, I, O. Now, we couple h separately with each
value of L'.
L' =2: 1£' l3lmin =I; L =3, 2, I (F, D, P);
L' =1: 1£' l3lmiJl =0; L =2, 1,0 (D, P, S);
L' =0: 1£' l3lmin =1; L =1 (P).
Overall, L = 3, 2, 2, I, 1, I, 0 (F, 2D, 3P, S  D and P occur two and three times,
respectively)
The case of l) = 1
2
= 2 is shown vectorially in Figure 6.27. In each situation the
resultant L shows the orientation of the combined quantized angular momentum
vector; its magnitude is obtained from the ClebschGordan series.
Spin angular momenta combine in a like manner to give the resultant spin value
S. A single electron has a spin quantum number of \11, so that the total spin angular
momentum S is also \11. The mu/tiplicity, or number of possible orientations of S, is
the value of 2S + 1. For a closed shell S is zero, and the state is referred to as a
(spin) singlet, with a term symbol 1S; it gives rise to a single spectral line in a
transition involving that state. Distinguish between S, total spin angular momentum,
and the term symbol S for the state corresponding to L = O. The superscript in the
term symbol is the multiplicity of that state.
The total angular momentum J for a multielectron species is given, as for j, by the
ClebschGordan series:
J = L + S, L + S  1, L + S  2, ... IL  51 + I,lL  51
We should note that when S is numerically greater than L, 2L + 1 terms arise from
the series, because J cannot be less than zero; thus, the doublet term 2S corresponds
to the one level 2S,,,. The SUbscript indicates the total angular momentum J: Na may
bewritten as [Ne] (IS)I, where [Ne] indicates a closedshell configuration equivalent
to that of neon, so that s = Y2 and 28 + I = 2; L = 0 (for an S state), so that J = L + S
= \11.
190 GrOUJl theory and chemical bonding
1 = 2
2
L = 3
[eh.6
1 = 2
2
1 = 2
1
L = 4 1 = 2
1
1 = 2
1
L = 0
1 = 2
1
1 = 2
1
Fig. 6.27 RussellSaunders coupling of two orbital angular momentum vectors I) = li = 2.
The resultant is shown by L limiting triangles are the line (L = 4), and the point (L = 0).
Transitions from states of multiplicity greater than unity lead to spectra that show
a splitting of the spectral 'lines' into two or more closely spaced lines. This splitting
arises because of the spinorbit coupling that we have been discussing, and is termed
fine structure in the spectmm. As an example, the configuration of sodium in the
first excited state is [Ne](3p)l, and in the ground state [Ne](3s)1. Inthe excited state
J (= j, because we are considering only one electron) can be 3/2 or Ih, and in the
ground state J = Ih only: thus, the doublet arises from the two transitions from the
two excited states of.! = 3/2, liz to the ground state of J = Ih, so that the yellow lines
for sodium correspond to the transitions
Sec. 6.7] GrOUI) theory and transitionmetal compounds 191
A quantum mechanical selection rule for spectral transitions denotes those
transitions that conserve angular momentum when a light photon is emitted or
absorbed. For oneelectron species, we have
Sn No restriction,
iiI = ±1,
lim, = O. ±l.
For multielectron species, analysis gives the rules:
M=O,±l, M=±l,
t1S= 0,
AI = 0, ±1 (0 ~ 0 forbidden).
EXAMPLE 6.5. This example considers several of the topics that we have just discussed.
(a) What total spin angular momentum and multiplicity would arise for an atom with four
unpaired electrons?
(b) What values of J may arise in the terms IS, 2p and '0, and how many states,
distinguished by MJ (M
J
= J, J  I, ..., .I), arise in each case? (MJ is the quantum number
associated with J
z
. ).
(c) Write term symbols for the transitions (i) Li: (IS)2(2p)1 ~ Li: (lsi(2si and (ii) Ca:
[Ar](3S)I(3p)1 ~ Ca: [Ar](3S)2; state the nature of the corresponding spectra.
(d) Write term symbols tor the species (i) K: [Ar] (3S)I, (ii) Ti'+: [Ar] (3d)1 and (iii) CI: [Ne]
(4pl
(a) 812 = SI + S2, SI + S2  I, ..., lSI  s21; Sm = s, +8
12,
S, +SI2 I, ..., Is, SI2!, and so on.
SI = \0'2, S2 = \0'2: 8
12
= 1, 0
S3 = \0'2,8
12
= 1,0: 8
m
=3/2, Y2, \0'2
S4 = Y2, Sm = 3/2, \0'2, \0'2: Sm4 = 2,1,1, 1,0,0:
8 =2: multiplicity 5;
8 = 1: multiplicity 3;
8 = 0: multiplicity I.
(b) J = L + S, L + S  I, .. , IL  SI.
The number of states is determined by lviJ.
IS: L = 0, S = 0, so that J = 0; ISO, 1 state.
2p: L = 1,8 = Y2, so that J = 3/2; 2p'l2 ,4 states;
J = \0'2; 2P
1/2,
2 states.
'0: L =2, S =1, so that.! = 3: '0
3
, 7 states (AiJ= 3, 2, ... 3);
J = 2; '02, 5 states;
J= 1; '0
1
, 3 states.
(c) (i) For Li: (lsi(2p)l, 1=1 and s = \0'2. For Li: (lsi(2s)l, 1= 0 and S = \0'2. Hence, 2p'l2 ~
2SI/2 and 2P
I
12 ~ 2S
1/2
; doublet.
(ii) Ca: [Ar](3S)I(3p)\ II = 0 and 1
2
= I, so that L = I; S = I, O.
For S = 1, multiplicity = 3; J = 2, I, 0 leading to 'P2 , 'PI and 'Po ('P2.1.0). For S = 0,
multiplicity = 1; J = 1 leading to 1PI.
Ca: [Ar](3si, L = I = 0 and S = () (closed shell) leading to ISO. Thus, 'PI,o ~ ISO is a doublet
(the transition from 'P
2
is forbidden by the selection rule 6J = 0, ± I); IPI ~ ISO is a singlet.
(d) (i) L = 0, S = \0'2 so that J = Y,: 2S1/2.
(ii) L = 2, S = Ii so that J = 5/2, 3/2: 20'12 , 2D,12
(iii) L = I, S = \0'2 so that J = 3/2, 1/2 2p,12 , 21'1/2.
192 Group theory and chemical bonding [Ch.6
In the transition series we have the important situation that the unpaired electrons
are in one and the same shell. Thus, we cannot use the quantum number n to ensure
that the Pauli exclusion principle is not violated, and other considerations come into
play. A discussion of this problem can be found in a standard work on atomic
spectra(29
J
, and Table 6.9 lists the states for the d" configurations of transition
elements under RussellSaunders (LS) coupling (see also Problem 6.20). We note
here that this mode of coupling is satisfactory for the first two transitions series, but
needs to be replaced by coupling for elements of higher atomic numbers.
6.7.2 How energy levels are split in a crystal field
In the compound [CO(NH
3)6]Ch
the central C0
3
+ cation is assumed, under crystal
field theory, to be linked to the NH
3
ligands through electrostatic forces of attraction
and repulsion, all subject to a certain symmetry, Oh in this example. It will be
satisfactory to work with just the rotations of point group 0 (Oh = 0 ® C
i
) and to
note that d orbitals are of even parity under inversion symmetry.
Table 6.9 States for d" configurations under LS coupling
n States
2, 8:
3, 7:
4, 6:
5:
"s, 1
D
, 1
G
, 3 p , 3
F
222 • 222244
P, 2 D ( D occurs tWIce), F, G, H, P, P, F
2
1
s, 2
1D,
1
F
, 2
1G,
1
1
, 2
3P,
3
D
, 2
3F,
3
G
, 3
H
, 5
D
2
S
2
p
2
D
2 2 2
H
. 2
1
4
p
4
D
. 4
F
4
G
6
S , ,3, 2 F, 2 G, , , , , , ,
The d orbitals of the central Co atom have the general form of (6.97): the radial
function R(r) is nondirectional and so is invariant under all pointgroup operations;
the function 8(8) in the spherical harmonic f(8, is invariant under all rotations
about the axis from which e is measured (the z axis). Thus, only the function <1>(<j» is
altered by rotational symmetry; this situation may be appreciated by reference to
Figure A5.l (see Appendix 5).
The general form of the <1>(<j» function is given by
<1>(<j» = exp(imJiP), (6.98)
and the five d orbitals correspond to the 2/  1 possible values of mi, as shown below:
m, 0 ±l ±2
Orbital d
z
2 d
yz
, d
zx
d
x
2.
y
2, d
xy
We may not assign m, values other than zero uniquely to d orbitals; the real
functions normally employed'Y' correspond to linear combinations of +m/ and m,
(Im/2l).
The function may be looked upon as an operator that rotates a vector
anti clockwise by the angle from the real axis in the complex plane. In Figure
Sec. 6.7] GrOUl) theory and transitionmetal compounds 193
(6.101)
(6.102)
The function exp(im,o<j» may be looked upon as an operator that rotates a vector
anticlockwise by the angle m,o<j> from the real axis in the complex plane. In Figure
6.26, for example, the real axis may be taken in the plane of m, = O. If, then, we
rotate the function exp(im,o<j» by an angle a, it becomes exp(im,o<j»exp(ia), or
exp[im/(<jl + a)]. The set of d orbitals under this transformation may be given as
A exp(im,o<j» = exp[im/ (<jl + a)], (6.99)
where A is the diagonal matrix
ilo: 0 0 0 0
e
0
i(1t)o:
0 0 0
e
0 0
i (12)0:
0 0 (6.100)
e
•
0 0 0
i (13)0:
0 e
0 0 0 0
ilo:
e
in which we have chosen to use the quantum number 1in the exponent in place of
mi. The difference from row to row is the multiplying factor exp(ia), and the
diagonal elements of (6.100) form a geometric series which sums in a general case
to give the trace XCJ.:
~ o : = exp(ilo:) + exp[i(l  1)0:] + ... + exp(ilo:).
= exp(ilo:){l  exp[i(21 + 1)0:)}.
[l  exp( io:)]
From de Moivre's theorem and halfangle formulae,
[I  exp(ina)] = 2i sin(na/2) exp(ina/2),
where n = 21 + I, so that, with standard manipulation,
Xa = =sin[(1 + '/2)a]/sin(al2).
For the d orbitals 1= 2, leading to
'X,CJ. = sin(5a/2)/sin(a/2).
We apply this result to the rotations of point group 0; thus,
xc, = sin(51t/3)/sin(1t/3) = I,
X
C4
=sin(51t/4)/sin(1t/4) = I,
X
C2
= sin(51t/2)/sin(1t/2) = 1.
For a = 0 (or 360°) we cannot use (6.102) directly, but by applying L'Hopital's rule,
Lt sin(aB) = Lt d[sin(aB)] = a[cos(aB)] = ~ .
B ~ O sin(bB) B ~ O d[sin(bB)] L t B ~ O b(cos(bB)] b
its limit as a ~ 0 is 5. This result is clear from the matrix (6.102) itself, and
corresponds to the character 'X,E . We have now the respresentation
194
o E
GroUI) theory and chemical bonding
6 C ~
[eh.6
5 I I
which reduces to E + T
2
, or E
g
+ T
2g
in the corresponding octahedral group ~ . It is
evident, then, that the five degenerate d orbitals are split under conditions of
octahedral symmetry into a doubly degenerate set spanning Eg and a triply
degenerate set spanning T
2g
•
The s orbital is fully symmetric and spans AIg , and the three p orbitals remain
unsplit and transform as T
l u
. A similar procedure can be applied to other groups,
such as the tetrahedral group T
d
, or the tetragonal group D
4h
; the totality of results is
collected together in Table 6.10. We may note that the symmetric nature of the sand
d orbitals is recognized by the 's' subscript in their irreducible representations
under Oh and D
4h
, whereas the p orbitals are anti symmetric and span 'u'
representations in these groups.
The relative dispositions of the energy levels e
g
and t2g are shown in Figure 6.28.
There is, of course, a close relationship to Figure 6.21, because the symmetry of
sulfur hexafluoride is also 0". However, in that example, we drew particular
attention to the large energy gap between eg and t2g in relation to the low chemical
reactivity of this compound. A significant feature of the transitionmetal compounds
is the relatively much smaller energy gaps between these levels, and manner in
which they change both with the nature of the ligand and with the pointgroup
symmetry. The magnitude of the energysplitting parameter I::;. among transition
metal complexes lies between leV and 3 eV, and for similar conditions of charge
and metalligand distance 1::;.0 (octahedral) is approximately twice I::;.t (tetrahedral).
Weak fields and strong fields
Transitionmetal compounds can be divided approximately into two groups: when I::;.
is small, say I eV or less, we speak of weakjield, or highspin, complexes, whereas
when I::;. is large, say 2.5 eV or more, we speak of strongjield, or lowspin,
complexes. Not surprisingly, there are intermediate situations, but the two limiting
cases will suffice for our purposes. The magnitude of I::;. is obtained usually from
spectroscopic measurements, so that a spectrochemical series of ligands may be
Table 6.10 Orbital splitting under Oh r; D
6h
and D
4
"
Orbital
0"
s A
19
P
z
}
P
x
T
lu
P
y
d 2
Z
E
d 2 2 q
X y
d
xy
d T
yz 2q
d
zx
A
1
T
2
E
D
6h
D
4h
A A
lq lq
A A
2u 2u
}
E
}
E
lu u
A A
lq lq
B
E
lq
2q B
2q
E
}
E
lq q
Sec 6.7]
Energy
r
Group theory and transitionmetal compounds
3d
e
t
2q
195
o SYMMETRY
h
DEGENERATE
d ORBITALS
r, SYMMETRY
Fig. 6.28 d Energylevel splitting under 01, and Td symmetry.
written, in increasing order of b.:
In the weakfield case, electrons are added according to the normal Aujbau
principle; the energy gap is small enough for Hund's rule to be obeyed over all d
orbitals. In the strongfield case, however, the larger value of b. results in the d
electrons being paired from the d
4
configuration: the crystalfield energy is
dominant.
Crystalfield theory provides an explanation for the form of the variation in
parameters such as the enthalpies of hydration of the divalent cations in .the (weak
field) halides of the first transition series. Figure 6.29 shows the plot of ,VMM
2
+,
aq) against atomic number for the first transition series. In Table 6.11, we show the
crystalfield stabilization energy (CFSE) for each of the weakfield complexes under
~ symmetry. The zero of energy for the CFSE here is the d" (d", d'") configuration.
An electron in a h
g
orbital is stabilized bv 2. b. with respect to the zero, whereas an
• 5
196 Group theory and chemical bonding [Ch.6
2000
3000
,
,
,
,
,
,
,
,
' ...
.....
....
.....
'
 ;
....
............ ,
.... ,
... ,
..... __/
Ca Sc ri V Cr Mn Fe Co Ni Cu Zn
Fig. 6.29 Variation with atomic number of the enthalpy of hydration of the divalent cations
of the first transition series.
Table 6.11 Crystalfield stabilization energies for weakfield complexes of the
transition metals under 0h symmetry
d Electrons Configuration Relative CFSE
0 (t
)0
(e
)0
0
2g
9
1 (t
) 1
(e
)0
2
8
2g
9
5
2 (t
)2
(e
)0
4
8
2g
9
5
3 (t
)3
(e
)0
6
8
2g
9
5
4 (t
)3
(e
) 1
3
8
2g
9
5
5 (t
)3
(e
)2
0
2g
9
6 (t
)4
(e
)2
2
8
2g
9
5
7 (t
)5
(e
)2
4
8
2g
9
5
8 (t
)6
(e
)2
6
8
2g
9
5
9 (t
)6
(e
)3
3

2g
9
5
10 (t
)6
(e
)4
0
2g
9
Sec 6.7] Group theory and transitionmetal compounds 197
electron in an e
g
orbital is destabilized by ~ . 1 : thus, we can calculate the CFSE for
5
the d
l

4
and d69 configurations, as shown in Table 6.11; the departures of the plot in
Figure 6.29 from the smooth curve are mirrored by the variation in the CFSE
values.
If, however, one plots the sublimation energy of the transition metal, or the sum of
that quantity and the ionization energy, M(s) ~ M
2
+(g), against atomic number,
then a similar 'doublehumped' curve is obtained. lt would appear that a
stabilization akin to that produced by a group of ligands occurs in the metal itself:
the symmetry around the metal ion in most elemental metals is 0h or D
6h
.
6.7.3 Correlation diagrams in Oh and Td symmetry
The splitting of the d levels is caused by the interaction of the metal with the ligand.
Thus, the magnitude and ordering of the splitting may be expected to change with
the degree of interaction.
The simplest situation occurs with a d' configuration. From Table 6.9 we see that
the state for the free ion is 2D, and Table 6.10 shows that this D state is split into E
g
and T
2g
under Oh symmetry; both states are doublets, because (L > S) with one d
electron the spin multiplicity is 2 in each state. A similar argument applies to the
tetrahedral symmetry T
d
, and the correlation diagrams are shown in Figure 6.30.
We tum our attention to species with two d electrons, such as [V(H20)6]3+, under
Oh symmetry. The situation is now more complicated, as we would expect from
Table 6.9. The freeion states are now IS, ID, IG, 3p and 3F, and the states for the
very strong interaction are obtained from a consideration of Figure 6.28 as (t2g)2 ,
(t2JI(eJI and (eJ2, in order of increasing energy. As the limiting strong field is
decreased the electrons couple in certain ways to give a set of states for the whole
configuration. The way in which the splittings on the righthand side of the final
correlation table (Figure 6.34) have been obtained depends on the direct product
relationships shown below, where we use again point group O.
198
<
Group theory and chemical bonding
 ...
/'

<>
29
o symmetry
h
[eh.6

T
d
symmetry
2
r
2
 1
It
2)
1
Ie)
FREEION
TERM
WEAKFIELD
INTERACTION
STRONGFIELD
INTERACTION
STRONGFIELD
CONFIGURATION
t) 11
Fig 6.30 Correlation diagram for a d
l
ion under Oh and Td symmetries; with d' there is no
problem over multiplicity.
0
E 8C 3C 6C 6C'
3 2 4 2
T ® T 9 0 1 1 1
2 2
T ® T 6 0 2 0 0
2 2
E ® E 4 1 4 0 0
By inspection, or from the standard reduction formula, we see that T
2
(29 T
2
reduces
to AI + E + T
1
+ T
2
, or A19 + E
g
+ T
I g
+ T
2g
in Oh. Similarly, T
2
(29 E in 0 leads to T
i g
+ T
2g
and E
g
(29 E
g
toA
1g
+A
2g
+ E
g
in Oh. Thus, we can set up the partial correlation
table, Figure 6.31; it remains to determine the multiplicities of the strongfield states
marked by an *.
Sec. 6.7] Group theory and transitionmetal compounds 199
We can achieve the desired result by using the method of descending symmetry.
Consider the state of (ei, and let the symmetry of the metalion environment be
lowered, say by a tetragonal distortion, to D
4h
. The degeneracy of the E
g
state is now
split, and inspection of the correlation table for Oh (see Appendix 11, Section Al 1.2)
shows that E
g
correlates with A
1g
+ Big. The two eg electrons may be placed in the
levels al gand bIg in 4!/(2!2!) ways, allowing for their indistinguishability, as shown
in Figure 6.32. It is clear that the states obtained from the a?g and b;g must be
singlets, since spinpairing leads to a multiplicity of unity. The configuration algb
lg,
however, may be either singlet or triplet.
We next consider how the states in D
4h
revert under Oh symmetry. Using the
correlation table again shows that IAIg and I BIg together ascend to E
g
, and IA
lg
remains as IAIg; a change in symmetry does not affect the multiplicity. The BIg state
(in D
4h
) has two electrons with unpaired spins and must, therefore, be the triplet
state 3B
1g
which ascends to 3A
2g
in Oh.
We can see that this result is to be expected. For (eg)2, we have (E ® E = AI +A
2
+
E)
(ei ~ xA
l g
+ YE
g
+ zA
2g
where x + 2y + z = 4!1(2!2!), or 6, as we have determined. Now, with two electrons
and two orbitals, x, y and z are each I or 3. First, y must be unity because it cannot
be 3 in the equation unless x = z = 0, which is not sensible. Thus, either x = 1 and z
= 3, or x = 3 and z = I; the former assignment was deduced from the above analysis.
200 Group theory and chemical bonding rcn.s
lA
1q

3
T
1q

3
A
2g
" ~ T
3 /
F / 2g
(
" 3
T
' ~

A
19
..
E '
q' 2
  ~ , r t )
T ~ ' : . .  ) ~
2g ~ ,
  ~ /
 /
T /
!.L/
FREEION
TERMS
WEAKFIELD
INTERACTION
Ii
o
STRONGFI ELD
INTERACT I ON
STRONGFIELD
CONFIGRATION
Fig. 6.31 Partial correlation diagram for a d
2
configuration under Oi. symmetry: the
multiplicities on the lefthand side are known from the term symbols; those on the right,
marked with an *, are to be deduced subsequently.
Sec. 6.7]
,'a
<' 19
2 ,
(e) '
9 b
19
Corre latlon ~
Equl valence ~
GrOUI) theory and transitionmetal compounds
H + +
+ + ++
1
A
1
B
3
B
1
A
19 19 19 19
r 1 1
1£
3
A
1
A
9 29 19
201
In Ot.
Fig. 6.32 Correlations tor (eg) in descending symmetry Oh ~ D4h. The e
g
level is split, and
the two electrons can be arranged on the two levels in tour ways. The terms arising in D4h are
then correlated with Oh with no change in multiplicity.
leading to lA
l g
+ 'u; + 3A
2g.
The case of (t2J
l(eJI
is straightforward, and a descent of symmetry is not
required. The spins are unpaired, so that singlet and triplet states are permitted.
Hence, from the direct product (T] ~ E = T
1
+ T
2
= T
2
~ E)
(t
2
!i (eJ ' ~ ]T
1g
+ 'T
2g
+ 3T]g+ 3
T2g
.
Finally, we consider the states arising from (t2
g
f from the foregoing we may write
(t2J" ~ "'Ajg+xEg+YTlg+zT2g,
where the multiplicities are connected by the relationship
w + 2x + 3y + 3z = 6!/(4!2!) = 15.
By trial and error with this result, it is easy to show that three assignments of
multiplicities are possible: we show them in the scheme below together with the
states of symmetry descent to ~ v .
The direct products involved with the (t2J
2
configuration are equivalent in ~ v to
the direct product of (.4
2
+ B] + B
2
) with itself. Thus, we obtain nine terms (ways of
arranging two electrons) that we group as follows:
w(A ) x(E) yeT ) z(T )
19 g 19 2g
{
1 1 1 3
POSSible
multl 1 1 3 1
p I I cit les
3 3 1 1
Equ I va I ence (A ) (A + A ) (A + B + B ) (A + B + B )
1 1 2 2 1 2 2 1 2
A ®A B ®B B ®B B ®B A ®B A ®B B ®B A ®B A ®B
1 1 1 1 1 2 1 2 1 2 1 1 2 2 1 1 1 2
A A A A B B A B B
1 1 2 2 2 2 1 1 2
1
;J; ;J; ;J;
A E T T
19 g
19 2g
202 Group theory and chemical bonding [Ch.6
We show this process diagrammatically in Figure 6.33, a scheme similar to that in
Figure 6.32 for (eg)" which shows that the terms are lA
1g
, lEg, 3T
1g
and IT
2g
.
It is now possible to complete the partial correlation diagram in Figure 6.31. In so
doing, we need to recall the noncrossing rule that we introduced when dealing with
symmetrydetermined cyclization reactions, and we add its further requirement that
symmetry states in the strong field must be connected to states of the same
multiplicity as the freeion (weakfield) states from which they originate.
*
t t t t
a
1
b
*
t t t t
2 1
(t )
+ + +
*
+
2g
b
2
Correlation
l
A
l
A
l
A
3
A
3
8
3
8
l
A
1
8
1
8
1 1 2 2 2 1 1 1 2
in C
2v
1 r
r r
Equi valence
l
A
1£
3
r
3
r
19 9
19
2g
in Oh
Fig. 6.33 Correlations for (hgi in descending symmetry 011 ~ C2v. The t2g level is split, and
the four electrons can be arranged on the two levels in four ways. The terms arising in ~ v are
then correlated with 0" with no change in multiplicity.
There is a third requirement, namely, that whereas symmetry states that are
represented once only on the diagram have energies that vary linearly with field
strength, when there are two or more states of the same designation they interact
and the linking lines are curved. The derivation of the correct curvature is complex,
and we employ straight lines in the correlation diagram, Figure 6.34.
The procedures that we have just discussed for 0h symmetry are equally applicable
to the point group Td. Typical tetrahedral complexes are the [CoC1
4
f ion and nickel
tetracarbonyl Ni(CO)4. Another important symmetry encountered in fourfold
coordination is the squareplanar configuration, symmetry D
4h,
as shown by [ptCl
4
f
or [CO(NH
3)4ChlCI.
Figure 6.35 is a correlation diagram for a d
2
compound under
T
d
symmetry, and Figure 6.36 illustrates the correlation between energylevel
splitting under octahedral and tetragonallydistorted squareplanar symmetries.
When two trans ligands are moved along their (z) axis a distance, away from true
octahedral symmetry, the distortion splits the dIevel degeneracy. For example, in
compression to D
4h
symmetry, the d.zlevel is raised in energy relative to the d
x
2.
y
2
level; d
yz
and d
zx
are raised in energy with respect to d
xy
. Under an elongating
distortion to D
4h
these energy changes are reversed. (How might these changes be
explained?) The true squareplanar configuration can be imagined to arise when the
trans ligands are elongated totally away from the ion; then, the d
z
2 energy level is
lowered significantly.
Sec. 6.6] Cyclization and correlation
203
l
A
~    ~   
(ll (ll

I
/
I
I
I
/
/
FREE ION
TERMS
WEAKFIELD
TERMS
STRONGFIELD
TERMS
STRONGFIELD
CONFIGRATIONS
Fig.6.34 Completed correlation diagram for d
2
species under OJ. symmetry, and also d
8
under
Td symmetry (drop the 'g' subscripts) where the strongfield configurations are (td(ei,
(td(ei and (t2)4(e)4. The figures in parentheses under the terms refer to the total degeneracy
of the states.
'Holes' in d orbitals
The procedures that we have used in studying the d
2
configuration can be used for
all d" configurations (2 s n s 9). In the d' case the single electron could occupy the
t2g orbital (the ground state) or the eg orbital (an excited state). With d
9
there are
again only two possible configurations, (t2g)6(eg)3 (the ground state) or (t2g)5(eg)4 (an
204 Group theory and chemical bonding icns
excited state). In the first of these two configurations all orbitals are filled except for
a 'hole' in e
g
, whereas in (
hJ5(eJ4
all orbitals are filled except for a hole in t
2g
. This
1
A
l(g)
1'
£ ,
\ r t )4(e )\(t )2
/I
T
"' ... 2g 9 2
/ OS)
1
T
/ /J
T
/
1(g) / / 1(g) /
/1' / / /
/ T(), / /
2g" //
1
e
/_<, »;
__,? 1£..... I
(9) '\' ... ...... (g)" / <,, II
\  I
" 1
A
'J'.
, 1 (g) / , <, 1
T
, / r >; .............. 2(g)
\ / /
\ / / , 1 (g) " 5 J 1
J / / J' (t
2
) (e ) ; (t e )
J T \ T '\__g_ 9 2
P l(g)/ J. 2(g)/'?(24)
/\ /
/
/ l(g)/
1 , ,/
T / / ,/
1 \ /.,/
1£ 7/
,/ \
" ,//
J , ,// ,
T A
r; \
J /'J
T
/" \
, \
(21)', J
A
"\
, 2(g) ,1
A
', "\ 1(g)
<, "1' 6 2 2
<, <, "£', (t, ) (e ) ; (e )
<, ,,(g), 2g 9
J "/"(6)
............ A /
..........
FREE ION
TERMS
WEAKFIELD
TERMS
STRONGFIELD
TERMS
STRONGFIELD
CONFIG URATIONS
) Ii
Fig.6.35 Correlation diagram for d
2
species under Te symmetry (drop the 'g' subscripts)
where the strongfield configurations are (td(e/, (td(ei and (h)4(e)4, and also dB under OJ,
symmetry. The figures in parentheses under the terms refer to the total degeneracies of the
states.
inverse relationship between d' and d", or d" and d
l O

n
is termed hole formalism.
Thus, we can obtain the correlation diagram for d
9
by inverting that for d', making
the highest state of d' the lowest state of d
9
, and so on.
A further relationship exists such that the d" configuration in 0h symmetry is also
the inverse of the d" configuration in Td symmetry. Thus, the correlation diagram in
Sec. 6.7] GrOUI) theory and transitionmetal compounds 205
Figure 6.35, which has been drawn for a d
2
configuration under T
d
symmetry is
applicable also to d
8
under point group Oh. Correlation diagrams have been
discussed fully in the literature [3134
1
•
• 2 2
B x Y_
1.
• 2 2
• 2 2 x__y B
....... __  19
• 2 ...
, z
.>===<
d 2 2 <,
X y ................. y
\ .
\ ..._XY_
B
d d
x y
\...  29
E .l!.. I' ,\
·.', / \
Zx , I \
, /
, yz I \
)=====( \
/ld
Z X'
XY
, \
I ','YZ \
/ .... d :... \
/ ZX , \ •
d / '\ ....E E
B !LI \ ·ZX •
~ \
d 2
~ A
I.
TETlL' COMA!.
(COttPRE5SI0N)
,Do.
OCTA.HEDRAL
TETR" CONAL
(ELaN C ;. TIOH)
,D
O.
TRUE SQUAR£_
PtA NAR
Do.
Fig. 6.36 Crystalfield energylevel diagram, showing the splitting of the dlevel degeneracy
by tetragonal distortion, In the true squareplanar configuration, the trans ligands are
assumed to becompletely removed.
6.7.4 Ligandfield theory
Ligandfield theory is the application of molecularorbital theory to the complexes
of transition metals. It allows for a delocalization of the d electrons of the central
metal ion into the orbitals of the ligand species, and the subsequent formation of
hybrid orbitals. We have considered some aspects of the linear combinations of
atomic orbitals for an ML
6
species, where M is a central species and L is a ligand: in
the example of sulfur hexafluoride, we saw the use of d orbitals in forming SF cr
bonds. Here, we examine this type of bonding more fully.
We assume that the metal atom can make use of its outer s, p and d orbitals, and
that the ligands contribute p orbitals to the bonding scheme, with their s electrons
forming a core. If we make a symmetryfree application of the LCAO method to this
group of orbitals, equation (6.35) would represent a 27 x 27 determinant. Instead,
however, we shall find the symmetryadapted orbitals that will reduce this
determinant to a number of smaller determinants.
We refer to Figure 6.37, where we have used the notation a, for the ligand orbitals
that form po bonds with the metal, and 1t, and rt , for the ligand orbitals that form
p1t molecular orbitals; the c, orbitals all have their positive lobes directed towards
the metal. We note first that no symmetry operation can interchange orbitals
between the metal and any ligand, so that we can write f
27
(the representation for
the complete determinant) as the sum of I'M , for the metal, and I'L for the ligands.
206 Group theory and chemical bonding [Ch.6
The s orbital of the metal is unmoved by any operation of Oh, so that it spans the
irreducible representation A19 • To study the p orbitals, we apply the method that we
used in Example 5.4 to give
E
3 o I I 3 o I I
We have enclosed certain symmetry operators in parentheses to indicate that they
are not essential in this application; we can use point group 0, provided that the
operator i is added in order to treat the anti symmetric p functions more conveniently
z
f
L
5
~
7 [ '
7[5 5
(j"
5
I
I
I
I
I
~ . ~
I
I
I
I
I
A
6
7['
6
7['
2
~ y
Fig. 6.37 Vector diagram for ligand pO" and p1t orbitals in an octahedral complex of general
formula ML6.
The respresentation [p is shown by the character table for Oh to be T
1u
. In a similar
way, we find for the d orbitals the representation
E
5 I 1
6C'
2
i
5
which is equivalent to E
g
+ T
2g.
Thus, for ru we obtain
[M = A]g+Eg+T2g+Tlu,
Sec. 6.7] Group theory and transitionmetal compounds 207
We consider next the reduction of f
L
for the ligand species. From Figure 6.37, we
can see that no symmetry operation of 0 (or 0h), acting through the origin M, can
convert a (Hype orbital to a 'Ittype orbital, although some 'It and 'It' orbitals are
interconvertible. It follows that a first reduction of f
L
is into I'; + f", where the
subscript 'It include both the 'It and 'It'type orbitals.
The part of the reduction concerning I', has already been carried out with the
example of sulfur hexafluoride. Thus, we have
I", = A, g + E
g
+ T,u ,
and the SALCs for cbonding have the same form as for that compound (see Section
6.5), and need not be repeated here.
We examine now the representation f", which is made up from six 'It and six 'It'
atomic orbitals, by applying the symmetry operations of 0 + i (or ~ ) to each orbital
in turn, remembering that the symmetry operations all act through the origin, at M.
We can set up the following scheme.
E: all orbitals are unmoved, so that XE = 12.
C
3
, C ~ , i, (8
6,84
) : all orbitals are moved, so that X=0 for these operators.
C
4
(z): 'Its ~ 'It; : 'It; ~ 'Its: 'lt6 ~ 'It ~ ; 'It~ ~ 'lt6. Similar results are obtained for
other C
4
operators, so that i:.C 4 =o.
C
2
(z): 'Its ~ 'Its; 'It; ~ n , ; 'lt6 ~ 'lt6; 'It~ ~ n ~ . Similar results are obtained for
other C
2
operators, so that X
C2
= 4.
(crh): 'Its , 'It; , 'lt6 and 'It~ arc moved; 'It; , 'It~ , 'It; and 'It ~ are unmoved; 'It) , 'lt2 'lt3
and 'lt4 are each inverted: thus, xcrh = 4  4 =o.
(crd): for the plane that contains z and bisects x and y, we see from Figure 6.37 that
'Its ~ 'It; and 'lt6 ~ 'It~ ; similar relationships exist for the other five crd planes, so
that xcrd =O. Thus, we obtain
f"
12 0 4 o
6C ~ i (88
o 0 0 o 0 o
which reduces to T
l g
+ T
2g
+ T
1u
+ T
2u
.
We could now use the projection operator technique to determine the SALCs, as
we have discussed in previous examples. However, we will use a shorter route in
this example, by finding those combinations of 'It and 'It' which, for the irreducible
representation under consideration, match the orbitals that span it.
The T
1u
irreducible representation is generated by vectors that behave like the e,
orbitals. From Figure 6.37, we see that along the direction of the x axis we have the
set 'It ; , 'It~ 'Its and 'lt6; thus, we can write the function
(l12)('It:, + 'It~ + 'Its + 'lt6)'
By referring to the y and z axes, we can write two other SALCs:
(l/2)('It; + n , +'It; + ' I t ~ )
(l/2)('It, + 'lt2 + 'lt3 + 'lt4)'
208 Group theory and chemical bonding [Ch.6
Application of the projection operator method would confirm the choice of these
functions. The T
Zg
representation is spanned by d
xy,
d
yz
and d
zx.
Figure 6.38
illustrates the d
xy
function using vectors to show the directions and polarity of the
orbitals. To reflect this d orbital, the ntype functions 1t 'I , 1t ~ , 1t ~ and 1t ~ have
been shown on the diagram. Thus, the function matching the symmetry properties of
dxy is given by 1t; , rr ~ , 1t ~ and rt ~ , so that we obtain
(l/2)(1t ;  1t ~ + 1t ~  1t ~ ).
Similarly for d
yz
and dzx, we have
(l/2)(1t3  1t4 + 1t ~  1t ~ ),
(l/2)(1t)  1tz +1ts  1t6).
We have now to consider the T
l g
and Tzu irreducible representations, for which there
are no counterparts in rM They relate to nonbonding energy states, and the T
l g
set
may be obtained from the character table for 0h, which shows that the degenerate
rotations R
x
, R; and R, span T
l g
. If we consider R
z
, Figure 6.39 shows the situation
for a rotation about the z axis. From the diagram, an anticlockwise rotation
corresponds to the set +1t; , rt ~ , rt ~ and +1t ~ , leading to
(l/2)(1t
1
 1t ~  1t ~ + 1t:
1
) •
•
L
4
rr:'
4
d
xy
d
xy
•
rr:'
3
L
3
x
rr:'
1 L
1
Fig 6.38 Vector diagram to show the d., orbital on the central atom M matching in phase the
retype ligand orbitals L
1L4
in bonding orientations.
For R, and R; similar functions can be developed:
(l12)(1t3  1t4  1t ~ + 1t6 ),
(l/2)(1t1  1tz  1ts +1t
o).
Sec 6.7] Group theory and transitionmetal compounds 209
n'
__ ~ 2
The functions that span Tzu must form an orthonormal set with the nine ligand
L
2
L
H
L
4 3
1[' 1['
4 3
L
n'
1
1
Fig. 6.39 A rotation vector R, , acting through M normal to the diagram, with the related 1t
type ligand orbitals LIL
4
.
functions obtained so far. If we write again the first ligand SALC that we derived,
namely,
(l/2)(1t ~ +1t~ + 1t5 +1t6),
it is not difficult to see that a new and satisfactory orthonormal funtion is
(l/2)(1t ~ +1t~  1t5  1t6),
and it is shown easily that it is, in fact, orthonormal to all other ligand ntype
functions. The remaining two functions may be devised in like manner:
(l/2)(1t; +1t~  1t5  1t~ ).
(l/2)(1t 'J + 1t  1t3  1t4).
It is a standard procedure, which we have already described in detail (see Section
6.3.4), to obtain the true molecular orbitals from these SALCs.
The 27 x 27 determinant has been now effectively broken down, through
symmetry, into a blockfactored matrix as follows:
A
I g
: one 2 x 2 block leading to two al
g
energy levels, and utilizing the metal s
orbitals and ligand pc orbitals. (Cumulative order, 2.)
Ti«: three 3 x 3 blocks, each leading to three triplydegenerate tl
u
energy levels, and
utilizing the metal p orbitals and the ligand po and p7t,1t' orbitals. Each block leads
to the same results so that only one need be solved. (11.)
E
g
: two 2 x 2 blocks, each leading to two doublydegenerate e
g
energy levels, and
utilizing on the one hand the metal dzz and ligand pc orbitals, and on the other hand
the metal dxzyz and ligand pc orbitals. (15.)
T
Zg
: three 2 x 2 blocks, leading to two triplydegenerate tz
g
energy levels, and
utilizing the dxy, d
yz
" d
zx
and P1t,1t' orbitals. (21.)
T
I g
: three I x I blocks, leading to the triplydegenerate tl
g
energy, and utilizing
ligand p1t,1t' orbitals. (24.)
210 Group theory and chemical bonding [Ch.6
T
2u
: three 1 x 1 blocks, leading to the triplydegenerate hu energy, and utilizing
ligand pn.n' orbitals. (Total order, 27.)
We see that the determinant of order 27 has been reduced to determinants of
orders 1, 2 and 3, which present relatively minor computational problems.
2a
19
p (3)
CENTRAL ATOM H MOLECULAR ORBITALS
pn (12)
peT (6)
s
LIGANDS L
Fig. 6.40 Molecularorbital energylevel diagram for an octahedral ML
6
compound. The
energy gap betweenthe 2hgand 2eglevels, oftencalledjust hgand eg, is &. The six pairs of
electrons indicatedin the lowerthree levelswouldfill six d
2
sp3 hybridorbitals.
A molecularorbital energylevel diagram is shown in Figure 6.40. The energy
levels from lal
g
up to leg provide strong o bonding, involving 12 electrons, egbeing
doublydegenerate. The 2t
1u
and lt
2g
levels consist of ligand ntype bonding
molecular orbitals, whereas t
2u
(lt
2u
) and t
1g
(ltlg) are nonbonding; these four levels
can accommodate 24 electrons, the ttypes being triplydegenerate. The 2t2g and 2eg
levels are atomic orbitals of the metal d orbitals, mixed with some ligand p and s
atomic orbitals, respectively. In a hybridorbital scheme they would comprise six
d
2
sp3 hybrids. The levels 3tlu and 2alg are strongly antibonding. The 2t
2g
and 2eg,
levels, often called just t2g and eg respectively, are of greatest interest in transition
Sec 6.7] Group theory and transitionmetal compounds 211
(a)
(b)
metal chemistry, and they will be discussed briefly under the headings of spectral
and magnetic properties.
The fourcoordinated transitionmetal compounds can be treated in an exactly
similar manner; the commonlyoccurring point groups are T
d
and D
4h
for sp3hybrid
type (tetrahedral) and dspihybrid type (squareplanar) complexes, respectively. Full
discussions of this subject are readily available[31
34
1.
Figure 6.41 shows the more important molecularorbital energylevels for a low
spin and a highspin complex. The levels are labelled in a commonlyused notation;
the upper t
2g
and e
g
levels correspond, respectively, to those labelled 2t
2g
and 2e
g
in
Figure 6.40. In the highspin (weak field) case, the small magnitude of the splitting
E I t \
t
! 4 \
I t 2 + '
Six ligand! ,.' g IItHi  ~ ~  _ . Five 3d orbitals
~ . . . . /tf
iii••~ . . . . . e / II
2p orbitals \'> g Iitt / I ~ I
\ , t, II
\ \ U HHH'/
\ II I
a,g
e
g
4
E / ~ l1LU",
t
Six ligand //.... t  ::1'J Five 3d orbitals
S ••K( e
2g
/:f
2p orbitals ""> g liB < ~ I
\ , t, U 1/
\ ' IHItt'/
\ II
a'g
Fig. 6.41 Molecularorbital energylevel diagrams for octahedral coordination. (a) Lowspin
(strong field) example, as with the ion [CO(NH3)6f+; the species is diamagnetic, with the
electron configuration (t2gt (b) Highspin (weak field) example, as with [Co(SCN)6t; the
species is paramagnetic, with the electron configuration (hg)4(egl
energy parameter ~ o is commensurate with the repulsion energy of paired electrons,
so that Hund's rule leads to singly occupied t2g and eg orbitals, with the result that
the highspin complex is paramagnetic, and the extent of the paramagnetic effect
depends upon the number of unpaired electrons present in the complex.
Spectral properties
The visible and nearultraviolet spectra of transitionmetal compounds are generally
assigned to transitions between the 2hg and 2e
g
energy levels, often called d ~ d
transitions. A reduced correlation diagram, known as an Orgel diagram, may be
useful in interpreting these spectra. Figure 6.42 is the Orgel diagram for d'
octahedral and related configurations: it may be compared with Figure 6.30.
Spectral transitions are normally subject to the spin selection rule, that t:.S = 0,
and the Laporte rule, that transitions between states of the same parity, 'u' or 'g',
212
Group theory and chemical honding [CIL 6
are forbidden. However, under spinorbit coupling relaxation occurs and symmetry
forbidden spectra appear, albeit with weak intensities. The Laporte rule depends
E
E
9









 _ T
29
E
o
d
4
, d
9
octahedral
d
1
, d
6
tetrahedral
~ ~ d
1
, d
6
octahedral
d
4
, d
9
tetrahedral
Fig. 6.42 Orgel diagram for some d electron configurations in octahedral and tetrahedral
synunetry.
upon the symmetry of the environment of the metal ion and, because of vibrational
movements within the species, the symmetry may not be strictly maintained. A
combination of the vibrational and electronic wavefunctions, vibronic coupling,
occurs, and d ~ d transitions of parity g ~ g are observed, with of low spectral
intensity, that are of particular interest in transitionmetal chemistry.
Figure 6.43a shows a portion of the electronic spectrum for the [Ti(H
20)6]3+
ion, a
d' species that is purple in colour. From the Orgel diagram, Figure 6.42, we assign
this weak transition as 2T
2g
~ 2Eg; it occurs at approximately 20300 em" (A == 493
nm). There is a shoulder at approximately 18500 ern", which arises from a splitting
of the 2Egstate by the symmetry of the ligand field. This spectrum is an example of a
Laporteforbidden transition arising through vibronic coupling (see also the Jahn
Teller effect, Section 6.5).
Figure 6.43b shows the spectrum for the ion [V(H
20)6]3+;
it is green in colour and
consists of low intensity bands at 17200 em" and 25600 cm' . They have been
assigned as follows:
1
25600 em
17200
1
em
3
T
(F)
19
3
r
(F)
19
A predicted transition 3T
1g
(F) ~ 3A
2g
(F) at approximately 36500 em" is not
observed because high intensity chargetransfer spectra occur in that region of this
spectrum.
Chargetransfer bands arise from transitions between the orbitals of the metal
atom and those of the ligands. In the hexacyanoferrate(II) ion [Fe(CN)6t, for
example, the transitions 1C ~ t2g and 1C ~ egarise. Because the transfer of electrons
Sec 6.7] GrOUI) theory and transitionmetal compounds 213
takes place between orbitals, higher energies are involved and the spectral
intensities are correspondingly greater than for d ~ d transitions.
In Section 7.6, we discuss some aspects of the group theory of electronic spectra
for transitionmetals compounds and other chemical species.
Intensity/relative
scale
5000 10000 15000 20000 25000 30000 35000
 1
v/cm
Fig. 6.43 Electronic spectra of solutions of transitionmetal complexes: (a) [Ti(H20)6t\
(3d)l; (b) [V(H
2
0 )6f +, (3df
Magnetic properties
When a sample of a chemical species is subjected to an applied magnetic field of
strength H (A mol), it undergoes magnetization of amount M (A mol) such that
M=K1l, (6.103)
where K is the volume magnetic susceptibility. (We give the units of magnetic
parameters because they are less familiar.) An alternative parameter is the mass
magnetic susceptibility X, defined by
X= KID, (6.104)
where D is the density of the sample, in kg m". The magnetic flux density B(T) is
governed by the expression
B = u, (l + K)H = Ilo(M + H), (6.105)
where u, is the permeability of a vacuum, and is defined as 41t x 10
7
(H mol or J c
2
mol S2). If, on the one hand, the magnetization M adds to the field strength H, K is
positive and the sample is paramagnetic. On the other hand, if M is opposed to H, K
is negative and the sample is diamagnetic. In fact, all substances show a
diamagnetic effect, which arises through an induced magnetic dipole. However,
when paramagnetism is present it dominates the diamagnetic effect. The permanent
magnetic moment that gives rise to paramagnetic properties develops from either
214 Group theory and chemical honding [Ch.6
electron spin or a combination of spin and orbital motion, in species containing one
or more unpaired electrons.
Magnetic susceptibility is measured on a calibrated Gouy balance, whereby a
cylindrical sample is suspended between the poles of a magnet. If the sample is
paramagnetic, the magnetic moments tend to be aligned with the applied field and
the effective weight of the sample is increased. If only diamagnetism is present, the
specimen moves out of the field and its effective weight is decreased.
The mass magnetic susceptibility of a species is given, by analogy with the
LangevinDebye equation[S3S4] for polarization, by
K =NJl<, [S + m
2
/(3k
B1)],
(6.106)
where Nis the number density of the species in m", S(J T
2
) is the magnetizability,
m (J T
1
) is the magnetic moment of the species, k
B
is the Boltzmann constant
(1.38066 J K"I) and Tis the absolute temperature.
In practice, we may replace K by XD, from (6.104), and since N = NA/V
m
= N
A
D/M
m
, where N
A
is the Avogadro constant, V
m
is the molar volume and M
m
the
molar mass (in mol kg") ofthe species, we have
X = (N
A
Jl<,!M
m
) ( [, + m
2
/(3k
B
1). (6.107)
If values of X are measured at different temperatures and plotted against liT, the
permanent magnetic moment m can be obtained from the slope of the line; the
inverse dependence of susceptibility on temperature is known as the (empirical)
Curie law.
Studies on the Zeeman effect!" J show that the permanent magnetic moment m
associated with a single electron of spin s is given by
m = 2ys, (6.108)
where y is the magnetogyric ratio, e/(2m
e
) . Quantum mechanics shows that s should
be replaced by the quantity [s(s + 1)]
Jl2
1i . Furthermore, magnetic moments are
usually expressed in units ofthe Bohr magneton = eli/(2m
e
) = 9.2740 x 10
24
J TIl, so that
m = 2[s(s + . (6.109)
In a multielectron species the spins combine; S =LS, whereupon
m = 2[S(S + . (6.110)
Applying this result to (6.106), neglecting the effect of S in comparison with m',
leads to
K = 4NJl<, S(S + /(3k
B1).
(6.111)
From (6.111), replacing K by XD and N by NAD/M.n, introducing numerical values
for the constants, and substituting Mill by M,./(lOOO/kg mol") where M, is the relative
molar mass, we find
X = (6.286 x 1O
3
/m
3
morJ){S(S+ 1)/[M
r
(TIK)]). (6.112)
EXAMPLE 6.6. In an experiment with a manganese coordination compound of molar mass
0.4333 kg mort and density 2150 kg m", the graph of X against liT, for measurements at
Sec. 6.7] Group theory and transitionmetal compounds 215
oDe, 25°e and 50
oe,
had a slope01'0.284 K. From(6.107), m = 5.60 x 10.
23
J T
1
or, in units
of the Bohr magneton, 6 . 0 4 ~ l B .
Usingnow(6.110), 2[S(S+ I)f12 = 6.04/18, so that S = 5.12/2, which corresponds, within
experimental error, to five unpairedelectrons. From(6.112) at T = 25°C, it follows that X=
4.26 x 10,7 m' marl.
So far, we have considered the spinonly contribution to the permanent magnetic
moment. Since S =LS, S =n/2 where n is equal to the number of unpaired electrons;
thus, the spinonly formula (6.110) may be recast as
111 = [n(n +2)]1/2
IlB.
(6.113)
For Example 6.6, this equation leads to m = 5.92, in close agreement with the
experimental value.
When there is a significant coupling of the spin and orbital momenta in a species,
and the ground state energy is separated from that of the excited state by an amount
that is large compared with kBT, the paramagnetic moment is given by
m = g[.J(.J+ l)f2
IlB
. (6.114)
where g is the Lande factor given by
g = 1 + [.1(.1 + 1) + S(S + 1)  L(L + 1)],
2.1(J + 1)
(6.115)
and .1is the total angular momentum obtained by the ClebschGordan series (see
Section 6.7.1). For a shell that is less than halffilled .J = IL  Sj; if it is more than
halffilled it is given by IL + Sj. From (6.115), we see that for S =0 (.1 =L) and g =
I, whereas if L = 0 (.1 = S) and g = 2. The latter result gives rise to the spinonly
formula (6.110).
The unpaired electrons in compounds of the lanthanons are well shielded from the
ligand (crystal) field, and (6.114) gives values of m that are mostly in good
agreement with experiment. Table 6.12.
EXAMPLE 6.7. We confirm the calculated values of", for Pr
3+
and Er+ in Table 6.12.
Pr+: L =5, S=1; J =IL  SI =4; from (6.115) g =0.8, and from (6.114)", =3.58.
Er+ : L =6, S =3/2; J =1L + SI =15/2; g =0.2, m = 9.58.
The poor agreements for Sm
3
+ and Eu3+ in Table 6.12 have been explained by a
more rigorous theoretical treatment'?", which led to values of 1.551lB and 3.40Il
B
,
respectively, for these two species.
216 GroUI) theory and chemical bonding [eh.6
Table 6.12 Magnet moments in ~ B for lanthanon sulphates
Ion Electron Term g m m
configuration symbol
calc expt
La
3+
(4f)o(Ss)2(Sp)6
1
5 1 0 0
°
Ce
3+
(4f) 1 (SS) 2 (Sp ) 6
2
F 6/ 7 2.54 2.39
5/2
Pr
3+
(4f)2(Ss)2(Sp)6
3
H 4/ 5 3.58 3.60
4
Nd
3+
(4f) 3 (SS) 2 (Sp l 6
4
1 8/ 1 3.62 3.62
9/2
Pm
3+
(4f) 4 (SS) 2 (Sp ) 6
51
3/ 5 2.68 2.83
4
Sm
3+
(4f)5(SS)2(Sp)6
6
H 2/ 7 0.84 5 1. 54
5/2
Eu
3+
(4f) 6 (SS) 2 (Sp ) 6
7
F 1 0 3.61
°
Gd
3+
(4f) 7 (SS) 2 (Sp ) 6
8
5 2 7.94 8.1
7/2
Tb
3+
(4f)8(Ss)2(Sp)6
7
F 3/ 2 9.72 9.6
6
Dy3+
(4f) 9 (SS) 2 (Sp ) 6
6
H 4/ 3 10.65 10.6
15/2
H0
3+
(4f)10(Ss)2(Sp)6
51
5/ 4 10.61 10.5
8
Er
3+
(4f)11(Ss)2(Sp)6
4
1 6/ 5 9.58 9.6
15/2
Tm
3+
(4f)12(Ss)2(Sp)6
3
H 7/ 6 7.56 7.5
6
Yb
3+
(4f)13(Ss)2(Sp)6
2
F 8/ 7 4.54 4.5
7/2
Lu
3+
(4f)14(Ss)2(Sp)6
1
5 1 0 0
°
Table 6.13 Magnetic moments in ~ B for transition seriesions
Ion Electron Term m m m
configuration symbol
(6.114) (6.113) expt
K+
(3d)o
1
5 0 0 0
0
Ti
3+
(3d) 1
2
D 1. 55 1. 73 1.8
3/2
v
3
+
(3d)2
3
F 1. 63 2.83 2.8
2
V
2+
(3d)3
4
F 0.77 3.87 3.74.0
3/2
Cr
2+
(3d)4
5
D 0 4.90 4.9
°
Mn
2+
(3d)5
6
5 5.92 5.92 5.9
5/2
Fe
2+
(3d)6
5
D 6.70 4.90 5.4
4
C0
2+
(3d) 7
4
F 6.54 3.87 4.8
9/2
Ni 2+
(3d)8
3
F 5.59 2.83 3.2
4
Cu
2+
(3d)9
2
D 3.55 1. 73 1.9
5/2
Zn
2+
(3d)10
1
5 0 0 0
°
Problems 217
In the first transition series the agreement is less good with equation (6.114), but the
spinonly formulae (6.110) or (6.113) give satisfactory results, Table 6.13. This
result arises because the d electrons in these species are less shielded than are the f
electrons in the lanthanons, so they interact with the ligands, which tends to quench
the orbital angular momenta.
The magnetic properties of coordination compounds are discussed in more detail
in the standard literature[31.3Z,54,551.
PROBLEMS 6
6.1 The overlap integral for two hydrogenlike Is atomic orbitals is given by SIs,Is =
exp(p)(1 + p + p
Z
I3), and for Is and 2p it is Sls,Zp = P exp(p)(1+ p + p
Z
I3), where p
is rta.; r being the internuclear distance. Plot both Sls,ls and Sls,Zp for r = 0 to 3ao.
Determine the value of the overlap integral SIs,1s for (a) H/ (r, = 0.11 nm) and (b)
Hz (z, = 0.074 nm), (c) At what value of (rlao) is the Is2p overlap a maximum?
Confirm this result by differentiation of the appropriate overlap integral function.
6.2 What are the ground state electronic configurations and bond order parameters K
for (a) Be and (b) C
z
. Which of these species is likely to be more stable than the
corresponding separate atoms?
6.3 Determine representations for the c and 1t bonding in the N
z
molecule using the
2p orbitals as a basis. Reduce the representations and formulate the normalized,
linear combinations of atomic orbitals used. What is the electron configuration for
the Nz molecule?
6.4 Work through the Huckel molecularorbital method for benzene (Section 6.3.1)
to obtain the SALCs, but use D
6
in place of C
6
; take C ~ through opposite carbon
atoms.
6.5 Trimethylenemethane C(CHzh is a known but unstable species. The central
carbon atom has three cr bonds and three 1t bonds. By applying the Huckel method
to this molecule show that the maximum total bonding power of a carbon atom is (3
+ ../3). Deduce the free valence for each atom.
6.6 Determine the SALCs and the coefficients and energies (in units of 13) for the 1t
molecular orbitals of naphthalene. Calculate the 1t bond orders, free valences, 1t
bond energy, delocalization energy, and write the nelectron configuration for this
molecule. What is the lowest energy transition for this species, and what is its value
(in units of 13)? Take the y axis through carbon atoms 9 and 10.
6.7 Apply the Htickel treatment to the 1t bonding of pyrrole, shown below. Let the
molecular plane be yz. Obtain the SALCs, 1t molecular orbitals, E,. and D".
H
N
/1""
HC 5 2 CH
"4 3" HCICH
218
Group theory and chemical bonding [Ch.6
6.8 Show that the two models for the lonepair hybrid orbitals of water (Section
6.4.1) leads to one and the same expression for the electron density.
6.9 Consider a rnolecule zld, of point group D
3h
. We have determined the SALCs for
cr bonding in this symmetry in Section 5.6.2. Determine the coefficients cij for a set
of hybrid orbitals <1>; (i = 13), where <1>1 = s, <1>2 = Px and <1>3 = py. List the hybrid
wavefunctions <1>]
6.10 The species [ptC1
6
f is assumed to undergo a symmetrical extension (Jahn
Teller distortion) of the two apical bond lengths. What is the symmetry of the
resulting species? Form irreducible representations using the new PtCI bond vectors
as a basis. (Let C
2
be along x, with (Tv the zx plane.)
6.11 Determine the LCAO molecular orbitals for the allyl cation (H2CCHCH2t,
using the pz orbitals normal to the molecular plane as a basis. Draw an energylevel
diagram for the molecular orbitals.
6.12 In Problem 6.11 we neglected any interaction between the end carbon atoms
(open threecentre bonding). Now assume that jjl2 = /323 (closed threecentre
bonding), so that 7t bonding can take place between carbon atoms 1 and 3. How is
the secular determinant modified. Draw a correlation diagram for the change 1312 =
o to jj12 = /323, assuming the variation to be linear. What can be said about the
change in stability and symmetry in the closed system?
6.13 In copper phthalocyanine, the copper atom is coordinated by four nitrogen
atoms of the phthalocyanine molecule; the point group is D
4h
. c Bonding arises in
the plane and 7t bonding normal to it. Find and reduce representations for these two
bonding modes. What is the nature of the hybrid cr bond orbitals? (Use the same
orientation of symmetry elements as in Problem 6.10.)
6.14 Construct the normalized wavefunctions for the Ti: state under 0h symmetry.
(The model used in Example 6.3 should helpful.)
6.15 (a) What is the total orbital angular momentum that may arise from the
combination of momenta in each of the following situations: (i) one p and one d
electron, (ii) one d and one f electron, and (iii) three d electrons? Give the term
letter for each case. (b) What are the term symbols for (iv) one d electron with spin,
and (v) two p electrons with spin?
6.16 What are the term symbols for the following electronic configurations: (a) CI:
(ls)2(2s)2(2p)6(3s)\3p)5; (b) Na: (lsi(2s)\2p)6(3s)l; and (c) Na:
(lS)\2S)2(2p)\3s)o(3p)l.
6.17 Write the d electron configurations for the d" species (n == 110) in weak and
strong octahedral fields. How many unpaired electrons are to be expected in each
case?
6.18 Solutions of the [Ni(H
20)6f+
ion (Oh) are light green, and the absorption
spectrum is shown in Figure P6.1; the freeion ground term is 3F. Use the Orgel
type diagram provided to make the most probable assignments to the transitions at
8700 em", 14500 em" and 125300 em"? Is there any feature of the transitions
worthy of comment?
Problems 219
Intensity/relative
scale
2
12000 16000 20000 24000
v/cm
1
E
A
T (P)
2q
1 T (P)
P 1q
T
1
(n
T
2q
T
2
T (F)
1q
A
2
0
d
2
• d
7
tetrahedral
~ 1 1 ~
d
2
d
7
octahedral
.
d
3
dB octahedral d
3
dB tetrahedral
. .
Fig. P6.1 Diagrammatic absorption spectrum of the [Ni(H20)6f+ ion, and the appropriate
Orgel diagram.
6.19 What ground state terms are to be expected for the electron configurations d' to
d
9
?
6.20 Confirm the asssignments of the terms to the d
2
(d") configurations in Table
6.9. Begin by considering how many ways two electrons with spin can be arranged
among the five d orbitals.
220 Group theory and chemical bonding [Ch.6
6.21 By considering how a regular tetrahedron is related in symmetry to an
octahedron, show what d orbital splitting is to be expected for tetrahedral
complexes. The [Zn(NH3)4f+ species has regular tetrahedral symmetry. The d
orbitals are split into egand t2g levels, with ~ t e t == 0.8 eV. Would the zinc compound
be diamagnetic or paramagnetic?
6.22 A coordination compound has a density of 2512 kg m" and a molar mass of
0.2822 kg mol". Its magnetic susceptibility K at 298 K was found to be 1.64 x 10
3
.
Given that the diamagnetic susceptibility is negligible, calculate Xin m
3
mol" and
the spinonly magnetic moment m in JiB; determine the number of unpaired
electrons in the species.
6.23 Consider the d
yz
and d
zx
orbitals of a coordination compound under 0h
symmetry. What is the effect on these orbitals and their energies by their rotation
through 90° about the z axis (a) in the absence of a magnetic field, and (b) in the
presence of an applied magnetic field? What d orbitals in the same example are
interconverted by rotations of 90° about (c) the x axis, and (d) the y axis?
6.24 Show that equations (6.105) and (6.111) are dimensionally correct. (Reference
56, or similar data, may be helpful.)
6.25 Rework Problem 6.4, but with C ~ passing through the midpoints of opposite
CH bonds. Compare the two sets of results: if they show a difference, how may it be
explained?
6.26 For the methylenecyclobutene species (see Section 6.3.3), (a) obtain a
representation based on the P: orbitals of carbon and reduce it, (b) obtain the true 1t
molecular orbitals, and (c) determine E".
6.27 The cycloaddition of two molcules of ethene to form cyclobutane is an example
of a DielsAlder reaction. If the molecular orbitals of cyclobutane are <PI a', <P2 air, <P3
a' and <P4 air, determine the conditions, thermal or photochemical, under which the
cycloaddition may occur. Use C" symmetry, with (jh passing through the centres of
the double bonds of ethene.
7
Group theory, molecular vibrations and
electron transitions
Like chords in unison they move,
And thrill with like vibration.
Thomas More (14781535): Sympathy: To Julia
7.1 INTRODUCTION: HOW A MOLECULE ACQUIRES VIBRATIONAL
ENERGY
Every chemical species possesses three forms of internal energy. In decreasing order
of magnitude, though not necessarily of importance, they are electronic, vibrational
and rotational in nature. In Chapters 5 and 6 we considered the electronic energy of
molecules and ions, and the part played by group theory in deducing acceptable
wavefunctions and in properties derived from them. We are able to apply group
theory to the vibrational motions of chemical species and to electron transitions
within them, and this study will form the essence of this chapter. Rotational energy
is not significantly dependent upon symmetry, and will not be discussed in detail
herein.
All chemical species execute vibrational motions at all temperatures. Even at
absolute zero atomic vibrations persist, as zeropoint energy. The vibrational
movements bring about transient changes in molecular geometry, such as bond
lengths and bond angles. but without causing a translation of the molecule as a
whole. Depending upon the state of the species, solid, liquid or gas, translations and
rotations may occur with vibrations. However, our present concern is with
translationfree, rotationfree (pure) vibrations. Radiation quanta in the infrared
spectral region have energies comparable to those involved in vibrational
transitions.
An atom is defined positionally in space at any instant by its three orthogonal
coordinates x, y and z. Hence, for a molecule containing n atoms there is a total of
3n such coordinates, or degrees offreedom. If the molecule as a whole is free to
translate, as a rigid body, and changes its position by a vector r, then this change
involves all positional coordinates:
r=ix+jy+kz. (7.1)
Furthermore, the molecule may rotate about an axis passing through its centre of
mass, and this movement may be resolved into rotations about the same coordinate
axes. Thus, of the total of 3n degrees of freedom for the molecule, six of these
degrees are involved in translation and rotation of the molecule as a whole. Hence,
the number of pure vibrations is 3n  6. In the particular case of a linear molecule, it
is conventional for one coordinate axis to be taken along the length of the molecule,
the internuclear axis. Rotation of the molecule about this axis does not alter the
222 GrOUJl theory and electron transitions [Ch.7
orientation of the molecule, and the moment of inertia for nuclei and electrons about
the internuclear axis is very small. Consequently, a linear species possesses 3n  5
true vibrations; a diatomic molecule has only one vibrational mode, corresponding
to a bondstretching motion.
A triatomic molecule, such as water, would be expected show three pure
vibrations; for carbon dioxide it would be four, and for benzene this number would
be thirty.
7.2 NORMAL MODES OF VIBRAnON
The internal vibrational motions of a molecule result from a superposition of a
number of vibrations known as normal modes. A normal mode is a natural vibration
of the molecule and has a particular frequency, something like the fundamental
vibration of a violin string. The sound of a violin string at, say, 440 Hz has a
different tonal character from that of a tuning fork resonating at the same frequency.
The fork produces an almost perfect sinusoidal vibration of the given (fundamental)
frequency, whereas the vibrating string contains a number of harmonics of the
fundamental vibration. The superposition of these harmonics on to the fundamental
produces the tonal character of the instrument. In a similar manner, the
superposition of the normal modes of a molecule lead to its characteristic vibration
frequencies. The frequency depends upon both the masses of the vibrating atoms
and the forces between them; a diatomic molecule has only one such frequency.
7.2.1 Symmetry of the normal modes
The number of normal modes is the number of degrees of freedom, which was
discussed in the previous section. We consider next the symmetry of the normal
modes, taking the water molecule as an illustrative example.
The vibrations of symmetryrelated atoms are related one to the other, so that the
normal modes may be given symmetry labels, such as AI and E. In Section 4.1.3, we
considered the r
3n
representation for the water molecule. From the three sets of
orthogonal axes, one set emanating from each atom, we constructed four 9 x 9
matrices to represent the actions of the symmetry operations of the point group ~ v
on each atom of the molecule, and developed the representation:
3 1
E
9
~ t    
r
3n
I
This reduces to 3A
I
+ A
2
+ 2B
I
+ 3B
2
. We may recall from Problem 4.4 that, with
the aid of the character table, we determined that the translational degrees of
freedom corresponded to AI + B
I
+ B
2
and the rotational degrees of freedom to A
2
+
B
I
+ B
2
; it follows that the (three) vibrational modes correspond to the sum 2A
I
+
B
2
. We note that the number of modes corresponds to the total dimensionality of the
irreducible representations for vibration.
We need next to associate the irreducible representations of the normal modes
with the internal coordinates of the water molecule. In relation to Figure 4.1, we
choose these coordinates to be the vectors r. and rb along the OH bonds, and a. for
the angle HOH. Using these internal coordinates as a basis, we generate the
representation
Sec. 7.2]
E
3
Group theory and electron transitions
3
223
Because no operation in C
2v
interchanges I" with n, we may write
The four 3 x 3 matrices for fVJ!,. based on the internal coordinates, are easily
blockedfactored: the example for the symmetry C
2
is given by
o
1
o
1
o
o
o
o
1
which leads to the character () for f. and I for I','> under C
2
. Thus, the r vectors and
the angle e1.. form 2 x 2 and I x I bases, respectively:
E
2
I
()
I
()
I
2
I
It is evident that f. reduces to AI + 13
2
, and that I'u: is the irreducible representation
AI.
H
a
H H
a
H
a
Fig. 7.1 Normal modes or vibration of the H
20
molecule: v, is the (pure) anti symmetric
bond stretch, and VI and V2 arc combinations of the bond stretch and angle deformation
movements.
Figure 7.1 shows the normal modes for the water molecule. The vibration labelled
Y3 is a pure, anti symmetric bond stretch. whereas those labelled VI and V2 are
compounded from both bondstretching and angledeformation modes.
We consider the molecule of boron trifluoride, point group D
3h
, as a second
example. The six normal modes for this species are shown in Figure 7.2. Each
normal mode forms a basis for an irreducible representation of the molecule, and
each of the vectors that represents an instantaneous displacement of an atom may be
compounded from these basis vectors. As we have seen in the previous example,
these basis vectors may be orthogonal coordinates centred on each atom, or internal
coordinates of the molecule related to bond lengths and bond angles. Figure 7.3
illustrates the molecule of SF:< with the orthogonal axes. The unshifted atom
224 Group theory and electron transitions [eh.7
V,
A;
E'
E'
Fig. 7.2 Normal modes or vibration of the SF, molecule. [Reproduced from 'Molecular
Spectra and Molecular Structure, Part 11, Infrared and Raman Spectra of Polyatomic
Molecules' by G Herzberg, with the permission ofthe publishers.]
contributions (see Section 4.1.3) leads to a f
J n
representation:
zc,
o 4 2
The [311 representation reduces to A ; + A ~ + 3E' + 24 ~ + E". From the character
table it is established readily that the translation and rotation functions span A ~ +
E' + A; + E": thus, I'VII> corresponds with A ; + 2E' + A ~ , which is correct for six
vibrations, because E' is a twodimensional representation.
In terms of the internal coordinates r and (X (all BF lengths and all FBF angles
are equal), we have
Sec. 7.2]
Group theory and electron transitions
225
Fig.7.3 Orthogonal sets of coordinates (x, y, z) and internal coordinates (r, ex) lor the BF,
molecule. The z axis is normal to the plane of the diagram, and the x axis is parallel to fl. All
operations of D'il act through the central, boron atom.
Thus, we obtain
E
3
3
ac,
()
()
3C:
3
3
()
()
r, = A ,+ E'
r",= A', +E'
It is evident that we have deduced 2:1; + 2E' instead, so that one result for A; is
spurious. The zl , representation in I', is satisfied, as shown by VI in Figure 7.2. For
r "', however, the representation A ; would require simultaneous, equal increments
(or decrements) in the angles (x. Accordingly, we discard the second A; result and
assign the A ; irreducible representation to the outofplane vibration V2. Spurious,
or redundant. cases like this arise with planar, tetrahedral and octahedral species,
where the bond angles form a closed set (sec Section 3.2.1): in the present case, a.3 =
360
0
 (a.I+ ex:). Furthermore. we note here that the normal modes that involve the
BF stretch and the FB F inplane bends are symmetric with respect to the ail
plane, so that all vectors involved in these modes lie in the symmetry plane. The
A ; symmetry is anti symmetric under Gil. and so does not involve the BF stretch
and FBF bend modes: a vibration mode for which the component vectors are all
perpendicular to the Gil plane corresponds to..1; in this point group.
We have shown in the above two studies that the normal modes of a chemical
species can be used to form bases for irreducible representations of its point group.
All wavefunctions for normal vibrations in the ground slate may be used as a basis
for the totally symmetric AJ typc representation of the point group of a molecule.
226 Group theory lind electron transitions [Ch.7
7.3 SELECTION RULES IN VIBRATIONAL SPECTRA
Vibrational frequency data on chemical species arise through infrared and Raman
spectra, and both techniques are normalIy employed in a vibrational analysis. In
infrared spectroscopy a beam of radiation, in the range 600 em" to 4000 em", is
passed through a sample of the species under investigation. The absorption at
different wavenumbers corresponds to excitation from the lowest vibrational level to
higher levels. Not all molecules respond to the infrared technique, and Raman
spectroscopy forms a complementary procedure. In this method, the sample is
irradiated with lasergenerated, (planepolarized) visible radiation. The molecule
may then scatter the radiation with a change in wavelength. On the one hand, when
the irradiating photons colIide with molecules and give up some of their energy, the
emergent, less energetic, scattered radiation is known as Stokes radiation. On the
other hand, when the photons colIect energy from the (excited) molecule in
collision, the higher frequency emission is calIed antiStokes radiation.
The appearance of infrared and Raman spectra are subject to selection rules that
are derived from a quantum mechanical analysis ofvibration
l3
1J.
7.3.1 Infrared spectra
The general selection rule for infrared spectra to be produced is that the molecule
possesses an oscillating dipole. When interatomic bonds in a polar molecule stretch
or bend, the oscillating dipole reacts on the electromagnetic field of the source
radiation and a part of it may be absorbed or emitted. Only those vibrations that
bring about a change in the dipole moment can lead to infrared spectra.
We can express this selection rule in terms of the integrals that we introduced in
Section 5.5. Let <Do represent the wavefunction of a molecule in the ground (initial)
state, and <Dr that of a final, excited, state of the species. The change in energy is the
fundamental transition <Do ~ <Dr, and the interaction between the molecule and the
radiation is the transition moment I, given by
= J<P'" I.l. <P d r ,
o f
(7.2)
where J.1 is the dipole moment vector of the molecule. If this integral has a nonzero
value, the transition will give rise to an infrared absorption line: it is said to be
infrared active. If, however, I = 0, the particular transition is infraredforbidden.
The dipole moment vector J.1 can be resolved along three orthogonal axes (see
Section 5.5), so that (7.2) may be broken down into three integrals:
t,
J
<P u , <P d r
o 1 f
(i = X, Y or z ) , (7.3)
where we use <Do because the groundstate wavefunction is real. It requires only one
of equations (7.3) to be nonzero for infrared activity to be possible, and this
condition we need to determine.
An integral (7.3) wilI be nonzero if the direct product of the irreducible
representations for the the two vibrational states is or contains the irreducible
representation to which J.1; belongs, and this situation can be judged with the aid of
Sec. 7.3] Selection rules in vibrational spectra 227
the character table for the point group of the molecule concerned (see also Section
5.5).
The vibrational groundstate wavefunction has the form of an s orbital, that is, it
is spherically symmetric, and belongs to a totally symmetric A Itype of irreducible
representation. Thus, in order to determine the infrared status, we need to form the
direct product ofthe representations of <1>0, u, and <1>r. We illustrate the this process
with the water molecule.
We have shown in Section 7.2.1 that the vibration modes for the water molecule
belong to the 2AI + B
2
combination of irreducible representations. From the
character table for e
2v
we find that the translational displacements along x, y and z,
that affect the value of the dipole moment, span B
I
, B
2
and Al respectively. Thus, we
need to know the symmetry of each component in an integral like (7.3), written
symbolically as
® ~ .
f
We now form direct products, where <1>0 spans A j , and <1>r spans Al or B
2
. For Al
symmetry, we have
A ®
f :: ]
® A
1
1
which leads to
A ® B ® A = B
1 1 1 1
A ® B ® A = B
1 2 1 2
A ® A ® A A
1 1 1 1
For B
2
symmetry, we have
A ®
f :: ]
® B
1 2
which leads to
A ® B ® B = A
1 1 2 2
A ® B ® B A
1 2 2 1
A®A®B =B
112 2
Thus, both the A I and B
2
vibration modes are infrared active. This short analysis
contains the general result that when <1>r has the same symmetry as one or more of
228
Group theory and electron transitions
[eh.7
the translational displacements x, y, z, and the initial state spans A I, then A 1 is
present in the direct product and the species can be infrared active.
Diatomic molecules
A diatomic molecule AB may be considered to behave like two masses m; and me
connected by a spring. If they are displaced in the direction of the bond between
them by a total distance x then, assuming Hooke's law, a force f is set up that tends
to restore the equilibrium position and which is proportional to the distance of
displacement; thus,
I = kx,
(74)
where k is known as the force constant for the bond between A and B, and the
system oscillates under simple harmonic motion.
Force is defined classically as the negative gradient of potential energy with
respect to distanceJ= dl/d.r , so thai
dl ' = kx dr. (7.5)
On integrating from x = 0 to a value r, we obtain, V = 'hk/ + c, where c is the
integration constant. At I' = r.; the equilibrium value, the potential energy is zero, so
that we have c = '/2kr ~ , and the potential energy expression has the form
(7.6)
(7.7)
The variation of the potential energy with interatomic distance is approximately
harmonic for small displacements from the equilibrium interatomic distance reo
The Schrodinger equation for this motion is
[ti
2
/(2f!) ~ : 2 + ~ k ( r  r
j
] \j! = E'.\j! .
where 11 is the reduced mass of the molecule, given
l
<; 2! by 1111 = (limA + lImB). The
solution! 193'; I of (7. 7), subject to the conditions that \j! + 0 as I' + 00 and that E is
quantized, leads to the energy levels
(7.8)
where o is the vibrational quantum number and ro = ...J(k/Il). For larger
displacements the vibrations become anharmonic, and the potential energy levels
arc better represented by the Morse equations:
V(r) =f)e{lexpla(rr
e
)J}2 (7.9)
where Deis the theoretical dissociation energy (including the zeropoint energy) and
a is a constant and
(7.10)
Sec. 7.3] Selection rules in vibrational spectra
V(r)/D
e
229
1
l       ~ 7 3
. ~
max
o
1
o
2
2 3 4 5
a t r  r )
e
Fig. 7.4 A Morse potential energy curve: the level at u = 0 corresponds to the zeropoint
energy, and the distance from this level to the continuum at V(r)/D
e
= 1 is the experimental
dissociation energy Do.
where x, is the anharmonicity constant given by x, = lia"/(2wo); the Morse potential
energy curve is shown in Figure 7.4. The selection rule for a harmonic oscillator is
t.u = ±I (7.11)
there being no restriction on the quantum number 11. For a transition u ~ u + 1, the
change in energy t.E
viI
) becomes
1)"E
vil
) = /iw  2(u +I )!iwx<
The radiation absorbed (or emitted) has a wavenumber ~ given by
u = uo2(u+ 1) u,,x<
(7.12)
(7.13)
where U
o
(J)/(2nc). Both (7.12) and (7.13) may be reduced to the harmonic
approximation by setting x, = o.
EXAMPLE 7.1. We examine the preponderance of the ground state in ill at 25°C. The
molecule has a bond force constant of 314 N m", and its reduced mass is 1.66 x 10,27 kg.
Thus, in the harmonic approximation, (I) = [314/(1.66 x lO,27)t
2
= 4.35 x 10\4 rad S·I, which
corresponds to a wavenumber of 2309 cm' (27.6 kJ mol"), which is clearly in the infrared
region of the spectrum.
Ifwe apply the Boltzmann distrihutiOlPXI, Iti =Itoexp(  ~ ; i IRT), to the two states u =0 and u
= 1 at 25°C, the ratio n.Jn, of the numbers of molecules in the two states is of the order of 7
x 10
4
, so that most ofthe molecules are in the ground state.
230 Group theory and electron transitions [eh.7
7.3.2 Raman spectra
The general selection rule for Raman activity in an irradiated molecule is that the
polarizability of the molecule changes as the species vibrates. The polarizability of a
molecule is a measure of the distortion of the electron density of that molecule by an
applied electromagnetic field, the source radiation in this application. A dipole is
induced in the molecule, by the field, and its moment J! is proportional to the
strength £ of the field:
J! = a£ (7.14)
where a is the polarizability of an isotropic species. In general, polarizability is a
tensor property governed by a 3 x 3 polarizability matrix au (i,j = x, y, z; CJ.ij = aJj).
Thus, there are six distinct components, the diagonal terms cu, and the offdiagonal
terms aij'
A species is Raman active if anyone of the six integrals Ii! is nonzero:
1
10
) 0 = J~ a: 0 0 ~ d'r
o 1) f'
(7015)
The specific selection rule for Raman spectra is t.o = ±l, where t.o = +1 leads to
Stokes radiation and t.o = I to antiStokes radiation.
We can examine a species for possible Raman activity by forming the direct
products from the symbolic expression
a: 2
X
a: 2
y
~
a: 2
® ~ ® Z
0 r
a:
xy
a:
yz
a:
zx
where the irreducible representations spanned by the aij terms are determined from
an appropriate character table. Returning to the example of the water molecule, we
found that the vibrations belong to the A] and B
2
representations, and the
corresponding product functions are seen to be x
2
, l, Z2, all spanning A], and xy, zx
and yz, spanning A
2
, B] and B
2
respectively. The relevant direct products are
A ® A ® A (B )
=
A
(B
2
)
1 1 1 2 1
A ® A ® A
(B )
=
A
(B )
1 2 1 2 2 1
A ® B ® A (B )
=
B
(A )
1 1 1 2 1 2
A ® B ® A (B )
=
B (A )
1 2 1 2 2 1
Sec. 7.3] Selection rules in vibrational spectra 231
from which it follows that both vibrations are Raman active. We will consider these
principles further in terms of examples.
EXAMPLE 7.2. We determine the infrared and Raman activity for (a) ammonia, NH3 (C3v),
and (b) benzene, C
6
Hti (D
6
h) with C ~ and cry orientated to pass through opposite carbon
atoms.
(a) We set up orthogonal x, y and z axes at each atom, and determine the number of unshifted
atoms for each operation of the point group, remembering that all symmetry elements pass
through the nitrogen atom. For NH3, we find:
E
12 o 2
. ® [ ;1] ®
A
1
A ® A ® A A
1 1 1 1
A ® E ® A E
1 1
A ® [ ;1] ® E
1
leads to
For E:
From the character table for C3v we find that the translations span A2 +E, and the rotations A2
+ E; thus, the true vibrations belong to 2AI + 2E.
Infrared
ForA
I
:
leads to
A ® A ® E E
1 1
A ® E ® E A + A + E
1 1 2
The molecule is infrared active, with two bands in its spectrum.
Raman
The product terms in C3valso span Al and E. Hence, the ammonia molecule produces two
bands in the Raman spectrum, coincident with those in the infrared.
(b) Proceeding in a similar manner for benzene, we deduce:
E 2C 2C C 3CI 3C"
6 3 2 2 2
r
3n
36 a a a 4 a a a a 12 a 4
which reduces to
[3" = 2Alg + 2A
2g
+ 2B2g + 2E1g + 4E2g
+ 2A2" + 2BI " + 2B2" + 4EI " + 2E2"
232 Group theory and electron transitions
[Ch.7
Nature
The translational and rotational displacements together span
A21I + E11I +A2g + El g
so that for the vibrationswe have
r vib = 2Al
g
+A2g+ 2E2g+ EIg+4E2g
+ A21I + 2EIII + 2E21I + 3EIII + 2E21I
The total number of modes thus represented is 30, which corresponds to 3n  6 degrees of
freedom for the 12atom molecule.
We may divide these vibrations into inplane and outofplane motions by consideringthe
behaviour of the characters of D6h under the O"h column: they are positive for inplane (i)and
negative for outofplane (0) vibrations; hence, we have
r = 2A + A + 4E + 28 + 28 + 3£
i 19 2g 2g 1u 2u 1ll
r =28 +£ +A +2£
o 2g 19 2u 2u
the sumof which restores r vib
Byforming the appropriatedirect products, as in the previous example, we obtain:
Infraredactive: A
21I
+ 3E
11I
Ramanactive: 2A
1g
+ Eig+ 4E2g
The reader is invited to confirm the above results and to show that the other
vibrations for the benzene molecule are infrared forbidden and Raman forbidden.
This example leads us to state a further selection rule, known as the mutual
exclusion rule: a molecule that is centrosymmetric cannot show both infrared and
Raman activity for anyone vibration mode. This result follows from the fact that the
translational displacements x, y and z are antisymmetric (u) under symmetry i,
whereas product terms, such as x
2
and yz, are symmetric (g) under i.
Polarization of Raman spectra
By examining the laserinduced Raman scattered light with a second polarizer, it
may be determined whether the scattered Raman radiation is polarized or
depolarized (the plane of polarization of the laser light rotated by 90°). A theoretical
treatment ShOWS[3537
j
that polarized Raman spectra arise from transitions that
involve the totally symmetric A Itype of vibrational mode, other transitions being
depolarized. Typically, the depolarized radiation has an intensity 75% or less than
that of the polarized radiation. In the examples that we have considered so far we
can add the following futher details:
Species Symmetry Number of lines
NH
3 Al 2
E 2
C
6H6
A
1g
2
E
i g
I
E
2g
4
Polarized
Depolarized
Polarized
Depolarized
Polarized
Depolarized
Depolarized
Sec. 7.4] Classifying vibrational modes
233
7.4 CLASSIFYING VmRATIONAL MODES
Group theory does not reveal the class of vibration, whether it is a stretching or
bending mode, but a number of general conclusions have been determined. We
consider again the water molecule, and the vibration modes illustrated by Figure
7.1. The vectors that determine the vibration modes are the internal coordinates of
the GH bond vectors r, and the HoH bond angle a.. We have shown in Section
7.2.1 that r r =A1 + B
2
and e" =AI. Thus, we expect two stretching frequencies for
rr and one bend mode for rex. The average values for the infrared and Raman
frequencies are listed below (in practice, there may be small, experimental
discrepancies):
Average I) Icm Raman nature
3650
1595
3756
Polarized
Polarized
Depolarized
1)1
HOH bend
HO symmetric stretch
HO asymmetric stretch 3756
We can assign the 3650 cm' and 1595 cm' vibrations to the Al symmetry, because
they are polarized in the Raman; thus, the 3756 cm' vibration belongs to B
2
. In
general, the stretching frequencies are higher than the bending frequencies in one
and the same molecule. Therefore, more fully, and in the light of Figure 7.1, we
conclude:
3650 em"
1595 em"
We consider next phosphorus pentachloride pels, point group D
3h
, as another
example in vibrational analysis. The experimental infrared and Raman data on a
solution in tetrachloromethane are listed below; some minor variations may be seen
for some modes in the infrared and Raman spectra that arise from random
experimental errors:
~ / c m I
Infrared Raman
581
444
579, depolarized
299
277
100
393, polarized
385, polarized
279, depolarized
261, depolarized
98, depolarized
234 Group theory and electron transitions
[eh.7
CI
CI
e
I a
""P'CI
e
CI
a
The molecule is trigonal bipyramidal, with two of the PCI bonds axial (a), along
the C
3
axis, and three PCI bonds equatorial (e) in the plane perpendicular to the C
3
axis. We set up orthogonal axes on each atom, and we derive r,n
4
2S,
2 4
3C
2
2
2Cj
()
E
18
1
f:l
which reduces to 21 1 + A', + 41'." + :VI; + 21'.'''. From the character table for D
3h
,
we find that the translations and rotations span E' + A ; + A; + E", so that r
vib
=
24 1 + + 24; + E". 12vibrations in all.
We consider bases in terms of the internal coordinates, first the axial bonds PCI.,
r, (remember that an unshiftcd vee/or contributes +I to XR, whereas a shifted vector
contributes zero):
2
()
3C
2
()
E
2
r" I
so that I', =/I 1 + A ; . For the equatorial PCI< bonds r, , we find:
:I
E
:.
r, I
2Sj
o 3
2C,
()
E
:I
so that I', ="1 ; + E'.
There are two types of bond angles that lead to bending modes, CIePCi
e
and
CIePCI
H
• We expect redundancies in each case because each set of angles is closed:
the equatorial angles (XI, (X2 and (X.3 arc related by (x" = 2rc  (0,1 + 0,2). For CIePCI
e,
we have
D
j h
'1 _
r::l
so that C< = A : + E'. For the CI<PCt angles, we find
2
() ()
E D3ht 1 _
r:1
so that rea = A ; + E' + /I; + E". In both of roe and C" the totally symmetric A;
cannot be present since the angles in a set (three or six) cannot be all changed
simultaneously by the same amounts.
Wc next examine the above information for infrared and Raman activity by
forming the appropriate direct products. For /'H, we need to consider:
Sec. 7.4] Classifying vibrational modes
235
for infrared activity, and
AI @
1
@ AI
1
(AI I )
2
@ AI
1
(AI I )
2
for Raman activity. It is evident that one product contains A ; in each case, so that
the PCl
a
stretches are infrared and Raman active. From the polarization data, the
infrared stretch is A ~ and the Raman A ; . Similarly, we find that the PCl. stretches
are infrared E' and Raman A ; (polarized) and E' (depolarized).
For the CI.PCl. angles we need to form direct products from:
for infrared activity, and
@ AI (E
I
)
1
@ AI
1
(E
I
)
for Raman activity. The products A ; ® E' ® E' = A ; ® (A; + A ~ + E') for
infrared, and A; ® A ; ® A ; and A ; ® E' ® E' = A ; ® (A; + A ~ + E') for Raman
indicate infrared activity for vibration E' and Raman activity for vibrations A; and
E'. However, we have indicated that the totally symmetric bend mode is not
possible, so we record the Raman A ~ as redundant. In a similar manner, we find for
f.
a
infrared activity (E' and A ~ ), and Raman activity (E' and E", both depolarized);
the A; result in the Raman is again redundant.
Summarizing the results so far, we have:
ro,
PCl
e
ctrci,
Stretch
Stretch
Bend
Bend
Infrared (A ~ )
Infrared (E')
Infrared (E')
Infrared (E', A ~ )
Raman (A ~ , polarized)
Raman (A ~ , polarised;
E', depolarized)
Raman (E', depolarized;
A; redundant)
Raman (E', depolarized;
E", depolarized;
A ~ redundant)
236
Group theory and electron transitions
[Ch.7
From a consideration of relative interactional energies we can now attempt to assign
the experimental frequencies to the modes that we have deduced. We expect that
symmetric stretches will be less energetic (lower in frequency) than asymmetric
stretches, and that axial stretches will be less energetic than equatorial stretches.
Again, we expect the bend modes to increase in frequency in the order
ci, rci, < ci,PCl
a
with one vibration for ClePCl
e
and three for ClePCl
a
. Thus, the following
assignments are indicated:
385 em"
393 em"
444 em"
579/581 em"
299 em"
277/279 em"
261 em"
98 em"
PCl
a
rcr,
ro,
rei,
circt,
ctro,
ct.rci,
ctrct,
Symmetric stretch (A ; )
Symmetric stretch (A ; )
Asymmetric stretch (A ~ )
Asymmetric stretches (E')
Bend (A ~ )
Bends (E')
Bend (E")
Bend (E')
7.4.1 Combination bands, overtone bands, and Fermi resonance
We have considered so far those transitions from the ground state <1>0 to an excited
state <1>[ by absorption of one photon of radiation: we referred to this process as a
fundamental transition. The vibrational energy levels for an natom molecule, in the
harmonic approximation, are given by[]7,35
j
3n
E = \'
vib L
i=l
1
(0\9. +  )hlJ.,
2 1
(7.16)
and in a fundamental transition one value of the quantum mechanical vibrational
quantum number is nonzero. It is possible for two normal modes to be excited
simultaneously: then a transition can occur to a combined level, where all o. but two
are nonzero. The energy value will be h(uJ + Uk ), where uJ and Uk are the two
relevant fundamental frequencies.
If the molecule gains two or more photons in one and the same vibration mode, an
overtone band arises with a frequency close to nu" where uJ is the fundamental
frequency and n is an integer; the approximation arises because the vibrations are
anharmonic. In both combination and overtone bands the energy levels are
degenerate, twofold degeneracy being the most common.
In some molecules an active fundamental vibration may be proximate to an
overtone or combination level. If their symmetries are different there can be no
interaction between them, but if their symmetries are the same an interaction known
as Fermi resonance takes place. Its effect is to increase the frequency of the higher
level and reduce that of the lower level, while equalizing their peak heights.
Sec. 7.4] Classifying vibrational modes
237
An example of Fermi resonance is shown by the Raman spectrum of
tetrachloromethane CCI
4
. For this molecule, point group T
d
, we can show, from the
principles already discussed, that four Raman bands should be observed.
Using five sets of displacement vectors, one set for each atom, we obtain:
E
15
which reduces to AI + E + T
1
+ 3T
2
. Eliminating the translational and rotational
components gives:
r
Vib
= AI + E+ 2T
2
By forming direct products, or by inspection of the character table for Td, we deduce
that T
2
is infrared active, and that AI, E and T
2
are Raman active. In terms of the
internal coordinates r (CH) and <X, (HCH), we can separate the true vibrations as
follows:
= AI + T
2
= (AI +)E+ T
2
E
4
6
T
d
I ~ 
r::l
c.
For reasons already discussed, the A1 mode in C. is spurious and must be
discounted. Thus, we find the following four Raman bands:
CCI Stretches AI, T
2
CICCl Bends E, T
2
I
1000
o
1
v/cm
Fig 7.5 Raman spectrwn of tetrachlorornethane; the intensity of the peak at ca 460 em"
indicates that it is polarized (AI).
From the experimental spectrum, Figure 7.5, we see that five bands are present, as
follows:
238 Group theory and electron transitions [eh.7
459
1
cm
Stretch
A
1
1
315 cm
Bend
T
1
2
217 cm
Bend
E
762
1
}
cm
1
Stretch
T
791 cm
2
The T
2
stretch has been predicted to occur at approximately 775 ern": now, the
combination ofthe 459 em" and 315 em" frequencies is 774 ern", and its symmetry
is that of the direct product AI (8) T
2
(= T
2
) . Thus, Fermi resonance takes place to
give two peaks of equal height, equidistant from the predicted value of 775 em".
While considering species with T
d
symmetry, we compare methane CH
4
with
monodeuteromethane CH
3D.
Methane belongs to point group T
d
, so that its Raman
activity follows the pattern for tetrachloromethane, that is, the activity is in the
modes A 1 + T
2
for CH stretches, and E + T
2
for bends.
Monodeuteromethane belongs to point group C
3v
, and the I'3" representation is
given by
E
15
C
3v
1,__
r:I
From the character table, we deduce that f
vib
= 3A1 + 3E. Using internal
coordinates, we have
I', = 2A]+E
ex. = (2)A1 + 2E
Now we can examine these results for infrared and Raman activity.
Infrared:
CH
4
A ® T ® A (E, T )
121 2
CH D
3
A
1
, E: Forbidden
T : Active
2
A
1
® [ ;1] ® A
1
(E)
A
1
, E: Both modes active
Raman
CH
4
A, ® [ ::] ® A, [E, T,)
A , E and T : All modes active
1 2
Sec. 7.4] Classifying vibrational modes
239
CH D
3
A ® [ A
l
) ® A (E)
1 E 1
A , E: Both modes active
1
Thus, C H ~ has the same number of infrared and Raman lines, whereas CIL has
one infrared and three Raman lines, which is sufficient to distinguish between the
two species.
7.4.2 Using correlation tables with vibrational spectra
We can take the deuteration process just considered one stage further and consider
the CH
2D2
molecule. Instead of carrying out the full analysis of the previous two
examples, we can use correlation tables, rather like we did in Section 6.6.
Monodeuteromethane, which we have just discussed, shows a decrease in
symmetry from T
d
(CIL) to C"" (CH
3D):
r, ~ C
3v
Al ~ A I
E 4E
T
2
4A
I
+E
Proceeding further to CH
2D2
(C
2v
) , we find:
Td >~ v
Al 4A
I
E 4A
I
+A
2
T
2
4 Al + B
I
+ B
2
It is now a straightforward matter to determine the infrared and Raman activities of
the CH
2D2
molecule, by direct products. What are they, and what situations would
obtain for the CHD
3
and CD
4
species?
7.4.3 Carbon dioxide as an example of a linear molecule
Carbon dioxide, an example of a linear molecule, belongs to the point group 'D""h,
and we expect four vibrational modes from this species. We set up orthogonal axes
at each atom, taking the z axis along the length of the molecule. Thus, we generate
the r 3n representation
r
3n
E
9
2Crp
00
3 + 6cos(rp) 3
i
3 1 + 2cos(rp)
roC
2
1
The results under C: and S: follow from the discussion in Section 6.2.3.
Although we cannot reduce this representation by standard methods (see also
Section 4.2.2), it is not difficult to see by inspection of the character table that r
3n
=
~ : + IT
g
+ 2L: + 2ITu .
240 Group theory and electron transitions [Ch.7
We now subtract the representations for translation and rotation, remembering
that rotation about the z axis does not constitute a degree of freedom in a linear
molecule, so that r vib = + + TIu .
f OlIC:O Symmetric stretch: V
1
= 1330
1
cm
Asymmetric stretch: v = 2349 cm
1
3
l' l'
l
Two bends, in and
normal to the plane
of the diagram: 667
1
cm
Fig. 7.6 Vibrational modes for carbon dioxide CO
2
Figure 7.6 shows the vibrational modes for carbon dioxide: if we form a
representation based on the C=O bond vector r, we obtain
o
«c
2
o o
•
2
oo@
v
2
2Cl{)
00
2
E
which represents the stretching modes, and reduces to + ; hence, the bend
modes are the degenerate TI
u
.
The irreducible representation spanned by z is : , and by x and y the degenerate
TI
u
and we form the appropriate direct products, as with earlier examples.
which expand to
+ + + +
® ® IT ) =
9 u 9 u u
+ + +
® IT ® o;. IT ) =
9 u 9 u u
IT )
u 9 9
IT (IT, + + )
u 9 9 9 9
[In the last product, the relation 4cos
2(cp)
= 2 + 2cos(2cp) will be useful.] Thus,
infrared activity arises for both the and TI
u
states. For Raman activity, we
investigate the direct products
which expand to
Sec. 7.5] Vibrations in gases and solids
241
~ +
®
~ + ®
~ +
( ~ , IT ) =
~ +
( ~ , IT
)
9 9 9
u u
9
u u
~ +
® IT
® ~ +
( ~ , IT ) = IT
(IT, ~ + ~ + tJ. )
9 9 9
u u
9
u u u u
~ +
® tJ.
® ~ +
( ~ , IT ) = tJ.
(tJ. , IT
+ q/)
9 9 9
u u
9
u u h
so that Raman activity arises for the L; mode. Summarizing: L; is Raman active
(polarized); we assign the L; to the symmetric stretch v, L: to the asymmetric
stretch v3, and the doublydegenerate Il, to the bend modes v2. The operation of
the mutual exclusion rule is evident in these results.
7.5 VIBRATIONS IN GASES AND SOLIDS
In a gas, molecules are free to rotate, so that vibrational bands are accompanied by
rotational fine structure. Each 'line' consists of a number of closely spaced
components of separation approximately Icm'. In simple molecules, rotational
spectra may be used to obtain details on the molecular geometry of the species. This
topic is not germane to this book, but an introduction to the topic may be obtained
from a standard text on physical chemistry'Y'.
In the solid state, strong intermolecular forces link the species so that they no
longer behave independently. It occurs frequently that a molecule belonging to a
given point group occupies a site in its crystal that is of lower symmetry. For
example, naphthalene CIOH
s
has the symmetry D
2lli
but in the crystalline state,
Figure 7.7, it occupies a site of symmetry C
j
, the centre of the molecule coinciding
with the centre of symmetry C
i
in the unit cell. In this situation, forbidden vibrations
for the free molecule may become active, and degenerate spectral bands may be
split.
We will say a little more about vibrations in the solid state in Section 8.7, after we
have discussed spacegroup theory; the vibrational spectra of gases, liquids and
solids is discussed authoritatively in the literature[3941
J
.
Fig 7.7 Stereoview of the unit cell andenvirons of the crystal structure of naphthalene, point
group D2h: the space group (q.v.) is P2/c with two molecules per unit cell, and the site
symmetry of the molecule is Cj.
242 Group theory and electron transitions [Ch.7
7.6 ELECTRON TRANSITIONS IN CHEMICAL SPECIES
The energies involved in electron transitions in molecules correspond to the visible
and ultraviolet regions of the spectrum, between approximately 20000 em" and
50000 em" in wavenumber. A study of electronic spectra leads to information on
the electronic structure of molecules, and permits an understanding of properties
such as the colour of chemical substances. We are concerned, here, with symmetry
aspects of electronic spectra; more general accounts of the subject are available in
the standard literature[38,
58
1. We shall consider the application of group theory to
electron transitions in some of the species for which we have already considered
their vibrational characteristics.
The interaction of the electronic structure of a molecule with radiation depends
upon its dipole moment, and is governed by (5.54). As with infrared activity, we
require the direct product associated with the integral f \Vi lla\Vf dr (ex, = x, y or z) to
contain the fully symmetric irreducible representation, for an electronic transition
from an initial state \Vi to a final state \Vfto be permitted.
We may recall here the Laporte rule (see Section 6.7.4). All wavefunctions are
either 'g' or 'u' in parity with respect to the centre of symmetry. Hence, because the
components of the dipole moment vector are all of 'u' parity in centrosymmetric
species (Why is this so?), the integral will be nonzero only if \Vi and \Vf are of
opposite parity (see also Section 6.1).
We explore the symmetry properties first with the water molecule. The molecular
orbital energylevel diagram, Figure 6.14, shows that the electronic configuration
may be written, omitting the 'core', as (la])2 (lb
2)2
(lb])2 (2b
2)o
(2a])o . For a
singlyoccupied molecular orbital the symmetry of the state is that of the molecular
orbital; thus, an a] molecular orbital is A], a b
2
is B
2
, and so on. If a molecular
orbital is fully occupied by two electrons, the symmetry corresponds with the direct
product A] ® A] =B] ® B] = ... =A]. If all occupied levels of a molecule are filled,
it has AItype symmetry as a whole.
The lower two electronic transitions for the water molecule are those for 1b, ~
2b
2
and lb, ~ 2a]; we refer to these transitions as n (nonbonding MO) ~ 0'*
(antibonding MO). The excited states corresponding to these transitions are (lad
(lb
2
i (Ib])] (2b
2)]
(2a])o and (la])2 (lb
2)2
(lb])] (2b
2)o
(2a])] , respectively. Their
symmetries are obtained by the direct products:
Ib, ~ 2 b 2 : (A] 0A]0)B] 0B
2=A2
; lb, ~ 2 a ] : (A]0A]0)B]0A] =B].
The symmetry of each excited state must be tested against (5.54), as we did in the
case of infrared and Raman activity. The dipole moment components in eN span A],
B] and B
2
. Thus, we have
Ib 7 2b :
At 0[ ::]
o A = A CB
2
, B J
1 2
2 2 1
2
Ib 7 2a : A
0[ ::] 0
B = B
CAl'
A )
1 1 1 1 1 2
2
Sec. 7.6] Electron transitions in chemical species
243
Hence, there is one possible n ~ 0* transition, lb, ~ 2al, in the electronic
spectrum of the water molecule, as is confirmed by the experimental finding of a
single band at approximately 170 nm.
7.6.1 Electron spin
In molecular orbitals that are occupied by a single electron, as with (lbl)1 or ( l ~ ) 1
in the first excited state of the water molecule, each electron spin s is Y2, so that the
state is a spin doublet. If a molecular orbital is filled, the electrons are paired, S = 0
and the state is a spin singlet. We have considered multiplicity in Section 6.7.1,
where we showed that a total spin S leads to 2S + I spin states. The spin selection
rule permits only those transitions that take place without a change of spin (see
Section 6.7.4), that is, where AS= O.
In the water molecule, the electrons in the singly occupied molecular orbitals in
the excited states can each have a spin of Y2. Since the allowed transition of (Ib.) ~
(2al), including spin, must be I AI ~ 1B
1
, it follows that the spins of the electrons in
(lb])1 and (2al)1 must be opposed, so that S = 0 and 2S + I = 1.
How term multiplicities combine
When we need to form direct products of terms that include spin, we must take
account of the multiplicities. Consider, for example, the direct product 2A
1g
18> 4A
2u
:
we know that the symmetry state of the product is A
2u
; the spin states will be a
Table 7.1 Combinations of multiplicities of terms
Term 1 (8) Term 2 ~ Product term
Singlet
Singlet
Singlet
Singlet
Doublet
Doublet
Doublet
Triplet
Triplet
Singlet
Doublet
Triplet
Quartet
Doublet
Triplet
Quartet
Triplet
Quartet
Singlet
Doublet
Triplet
Quartet
Singlet + triplet
Doublet + quartet
Triplet + quintet
Singlet + triplet + quintet
Doublet + quartet + sextet
triplet and a quintet, as the following argument shows.
Two spins S, and S;. are added according the ClebschGordan series (see Section
6.7.1) to give S, + S;, S, + S; I, ..., lSi  S;.I. For a doublet and a quartet, say, S, and
S; are Y2 and 3/2, respectively. The resultant spins S are, therefore, 2 and 1, giving
multiplicities of 5 and 3, respectively. In this way, we can work out all such
combinations, and a selection of those most commonly met is listed in Table 7.1.
7.6.2 Electron transitions among degenerate states
In Section 6.3.1 we studied benzene by the Huckel molecularorbital method, and
Figure 6.6 is a molecularorbital energylevel diagram for this molecule. The lowest
energy transitions involve the elg1t molecular orbital, and the first of them is elg ~
244 Group theory and electron transitions [Ch.7
e2u. The ground state of the molecule may be written concisely for our purposes as
(a2u)2 (elg)4 ; it hasA
lg
symmetry, and is a spin singlet, IA
ig.
The excited state is (a2u)2 (elg)2 (elg)3: a2u is filled, so that its symmetry is AIg, and
e2u has symmetry E
2u
. We need to determine the symmetry of (elg)3: a rule derived
from quantum mechanics states that when a molecular orbital, capable of being
filled by a total of n electrons, is more than halffilled, with a number p of electrons,
it may be treated as a molecular orbital containing n  p electrons. In the present
case we write it (eli; it is as though the degenerate orbitals are here separate, with
one of them corresponding to A1g Thus, we need the direct product (A
l g
181) E2u 181
E
2u
; A
l g
merely multiplies each term by unity:
D
6h
E 2C
6
2C
3
C
2
3C ~ 3C ~ i 2S
3
2S
6
O'h 30'd 30'h
2 1
2 I
1
1
2
2
o
o
o
o
2 1
2 1
1 2 0
1 2 0
o
o
1 4 o o 4 1 1 4 0 o
Thus, E
ig
181 E
2u
reduces by standard methods to Bi; + B
2u
+ E
1u
, which may be
confirmed from Section Al 1.3 (Appendix 11).
The spins of (elg)3 and (e2u)1 are each Y2, so that S is 0 or 1. Thus, we can postulate
the spin states IB
lu,
3
Blu
, IB
2u
, 3B
2u
, lE
lu
and 3
Elu.
The (orbital) symmetryallowed
states are obtained from the appropriate direct products. In point group D
6h
, the
translational displacements span the irreducible representations A
2u
and E
lu
; thus,
we form the direct products
A
ig
I8IA
2u
181 s.; (B
2u
, E
l u
) = Big (B
2g
, E
2
g)
and
A
ig
181 Ev« 181 Be; (B
2u
, E
l u
) = E
l g
(E
2g
, A
l g
+ A
2g
+ E
2
g)
The only symmetryallowed transition isA
lg
~ E
lu;
including spin, we write IA
lg
~
lEI u , so that the lowenergy region of the electronic spectrum of benzene will show
a single band. This transition is termed 7t ~ 7t* , and occurs with high intensity at
approximately 180 nm.
There are situations where forbidden transitions are observed, as we have already
discussed in Section 6.7.4. Their study is complex and lies outside the scope of this
book, and the reader is directed to the standard literature[29,33,38
1
.
7.6.3 Electron transitions in transitionmetal compounds
In Section 6.7.3ff we considered crystalfield results on coordination compounds,
particularly the d' and d
2
configurations. Some aspects of electronic transitions in
these compounds were touched on there, and here we consider applications of group
theory to electronic transitions in these compounds.
The concise configuration for a d' compound under T
d
symmetry may be written
as (e)' (t
2
)0 and under Ohsymmetry as (t2g)1 (eg)o . We consider tetrahedral symmetry
first. The only transition is (e)' ~ (t
2)1.
The symmetries of the two states are E and
T
2
, and the spin state is 2 for each. The spinallowed transition is, thus, 2E ~ 2T
2.
Problems
245
The dipole moment components span T
2
in T
d
, so that we need to form the direct
product
E 0 T
20
T
2
= (T
I
+ T
2)
0 T
2
= Al +A
2
+ 2E + 2T
I
+ 2T
2
;
thus, the d ~ d transition 2E~ 2T2is fully allowed.
If we consider the same configuration under ~ symmetry, we have (t
2g)1
~ (eg)l,
with corresponding symmetries T2gand Eg. The direct product now is
T2g0 Ts« 0 Eg = (A
2u
+ E; + Ts« + T
2u)
0 Eg = A
l u
+A
2u
+ 2E
u
+ 2T
l u
+ 2T
2u,
so that d ~ d transitions are symmetryforbidden. If we consider the spin states, the
initial state is 2T
2g
and the final state is 2E
g.
Thus, although d ~ d transitions are
forbidden by parity (see Section 6.7.4), breakdown ofthis rule does permit the (spin
allowed) transition 2T
2g
~ 2Eg, albeit of very weak intensity.
Turning now to complexes of d
2
configuration, under T
d
symmetry we have the
transitions (e)2 ~ (e)l(t2)1 and (e)2 ~ (ent2)2. The relevant symmetries are Al + A
2
+ E for the initial state, and (T
l
+ T
2)
and (AI + E + T
I
+ T
2)
for the two excited
states. From Figure 6.35 and the attendant discussion, the ground state was shown
to be 3A
2:
the spin states for the excited levels are IT
l,
3
T1,
IT
2,
3T
2,
and IAI, IE, 3T
I,
lT
2.
Thus, we need to consider the symmetryallowed transitions between triplet
states, bearing in mind that the dipole moment components span T
2
in T
d
. Thus, we
evaluate the direct products
A
2
0 T
2
0 T, = T, 0 T, = AI + E + T
I
+ T
2,
A
2
0 T
20
T
2
= T
I
0 T
2
= A
2
+ E + T
I
+ h
Hence, the transitions 3A
2
~ 3T
h
corresponding to (e)2 ~ (e)l(t
2)2
and (e)2 ~
(t
2)O(e)2,
are fully allowed, and will lead to intense bands in the electronic spectrum;
the spinallowed, symmetryforbidden transition 3A
2
~ 3T2 may give rise to a band
of relatively very weak intensity (see Section 6.7.4).
Under ~ symmetry, all d ~ d transitions are forbidden under the parity selection
(Laporte) rule. However, where the symmetry restriction breaks down, the spin
allowed transitions may be observed with weak intensity. The ground state of d
2
species under 0h symmetry is 3T
Ig
(see Figure 6.34): the excited states correspond to
IT
Ig,
3T
lg,
IT
2g,
3
T2g,
and IA
Ig,
3A
2g,
's, Thus, the spinallowed transitions are
3T
lg
~ 'r., 3
Tlg
~ 3
T2g
and 3T
Ig
> 3A
2g.
This behaviour is exhibited by the
[V(H20)6 ]3+ species, for example, and the transitions above have been assigned the
wavenumbers, in order, 25600 em", 17200 em" and 40000 em". The reader may
wish to recall the material in Section 6.7ff, and to extend his studies to some of the
standard literature on transitionmetal chemistry[3I'34,41.58
l
.
PROBLEMS 7
7.1 How many vibrational modes are to be expected for each of the following
species? (a) hydrogen chloride, (b) carbon oxysulfide, (c) nitrogen dioxide, (d)
carbonate ion, (e) monochloromethane, and (f) anthracene.
7.2 A molecule of general formula lvfX
2
may be linear or bent. What vibrations are
infrared active and Raman active in each case?
246 Group theory and electron transitions [eh.7
7.3 Benzene belongs to point group D
6h
. The symmetric CC stretch mode is
allocated toA
lg.
Is it infrared and/or Raman active in this mode?
7.4 The BF
3
molecule was studied in Section 7.2.1. Consider the data below, and
assign the given frequencies to the vibrational modes.
~ / c m I
Infrared Raman
V1 888
692 V2
1454 V3 1454
480 V4 480
7.5 Trichlorophosphine oxide ChP=O has the same symmetry as ammonia.
Determine representations in terms of the internal coordinates. What are the
symmetries of the infrared active and Raman active vibrations?
7.6 The average experimental infrared and Raman frequencies of
trichlorophosphine oxide (see Problem 7.5) are listed below. Allocate the
frequencies to the infrared and Raman modes found.
Raman nature
1291
Polzd.
581
Depolzd.
487
Polzd.
339 267
Depolzd. Polzd.
193
Depolzd.
7.7 A JahnTeller distortion along the z axis of the octahedral complex [CoC1
6
]3
reduces its symmetry to D
4h
. What are the symmetries of the infrared active and
Raman active modes of the complex of lower symmetry, and can these spectra be
used to distinguish between this complex and the true octahedral form?
7.8 What are the infrared active and Raman active vibrational modes of benzene?
How would the spectra be affected by contamination of the benzene sample with
monochlorobenzene?
7.9 Reconsider Problem 7.8, starting with [yib (benzene), and using the correlation
table for the decrease in symmetry from D
6h
to C2y.
7.10 By means of correlation tables, deduce the symmetry of the vibrational modes
of PC1
4Br,
using data on PCls in Section 7.4. Consider the bromine atom in (a) an
equatorial position, and (b) an axial position.
7.11 The molecular orbitals of methane may be written as (la1)2 (lt
2
/ (2al)o (2t
2
f
What are the excited states for the It
2
~ 2al and It
2
~ 2t
2
transitions in methane?
How many 0 ~ 0* transitions are fully allowed in this species?
7.12 The first four 1t molecular orbitals of butal,3diene may be written as (la
u)2
(lbi (2a
u)o
(2bg)°. (This notation is slightly different from that used in Section 6.6,
but is often encountered.) What 1t ~ 1t* transitions are expected for this molecule?
7.13 Infrared spectral bands for HC=N are observed at 3311 ern", 2097 em" and
712 em". Determine the number, symmetry and activities of the fundamental
Problems
247
vibrations. Assign the frequencies to the H ~ C stretch, C ~ N stretch, and bend
modes.
7.14 The infrared and Raman spectrum for the [HF
2
r and [DF2r ions, investigated
as their potassium salts, are listed below. (a) Are the ions bent or linear and what
are their structures? (b) Sketch the normal vibration modes. (c) Assign the
frequencies to the modes.
 1
vlcm
Infrared
1550
1200
Raman
675
Infrared
1140
860
Raman
675
7.15 What terms are obtained from the configuration (elg)2 (e2U)2 under D6h
symmetry?
8
Group theory and crystal symmetry
For true understanding, comprehension ofdetail is
imperative. Since such detail is wellnigh infinite
our knowledge is always superficial and imperfect.
Due Francois de la Rochefoucauld (16131680): Maxims
8.1 INTRODUCTION: TWO LEVELS OF CRYSTAL SYMMETRY
Crystal symmetry may be viewed on two levels: a crystal, as a finite body, is
described in symmetry by one of the crystallographic point groups that we studied in
Chapter 3, whereas in terms of a regularly repeating unit containing chemical
species it is specified by a space group. Although spacegroup theory applies,
strictly, to an infinite arrangement of the species in a crystal, we may use it in this
context because, under normal experimental conditions, the number of repeating
units is very large in the crystal under examination. For example, a crystal of
sodium chloride of dimensions O. L 0.1, 0.1 nun contains approximately 5.6 x 10
15
repeat units of structure.
8.2 CRYSTAL SYSTEMS AND CRYSTAL CLASSES
The gross classification of crystals is carried out in terms of crystal systems. There
are seven crystal systems, and each is characterized by a certain minimum symmetry.
Table 8.1 lists the system names and their characteristic symmetry: we use here both
the Schonflies notation, with which we are familiar, and, in parentheses, we begin
to introduce the HermannMauguin symmetry symbols for crystal symmetry. In
Table 8.1, the characteristic symmetry has been given in terms of axes, rotation and
rotareflection (and rotainversion), but we recall from our earlier discussion that SI
is equivalent to cr (with cr 1 S\), and 8
2
to i (with i on the S2 axis). The trigonal
system has been referred here to the same set of reference axes as has the hexagonal
system; otherwise, the threefold axis in the trigonal system would be along a vector
Table 8.1 The seven crvstal systems and their minimum symmetry
System name Characteristic, minimum symmetry with orientation
Triclinic None
Monoclinic One C
2
(2) or one S\ (:2 ), along y
Orthorhombic Three mutually perpendicular C
2
(2) and/or S1 (2'), along x, y and z
Tetragonal One C
4
(4) or 8
4
(4 ), along z
Cubic Four C
1
(3), at cos" (1..}3), or 54.74°, to x, y and z
Trigonal One C
1
(3), along z
Hexagonal One C
6
(6) or S, ( 6 ), along z
Sec. 8.3] Why another symmetry notation 249
(a + b + c), the full meaning of which will be clear shortly. A given crystal may
possess more symmetry than that characteristic of its system.
In crystallography, the reference axes x, y and z follow the pattern discussed in
Section 2.3, but they are not necessarily orthogonal, because they are selected so as
to coincide with the symmetry axes of the crystal; the conventional choices are listed
in Table 8.2.
Crystal class is a morphological term related to but not the same as point group.
Thus, crystals of a given point group belong to one and the same crystal class. A
class is a sort of classificatory pigeon hole, and should be differentiated from the
symmetry class as discussed in Section 3.2.5ff.
Table 8.2 Interaxial angles in the crystal systems
System name Interaxial angle relationships
Orthorhombic I
Tetragonal Axes (x, y, z) orthogonal.
Cubic
HexagOnal} . °
. .. Three equivalent axes, x, y and u, at 120 one to
Tngonal the other, and in the ~ plane, .1z axis.
Trigonal x/\y = y/\z = ZX '* 90°. < 120° (trigonal axes).
Monoclinic y.l zx plane (by convention); xy = ~ z = 90°;
zxcan take any value, normally '* 90°, 120°.
Triclinic x/\y, y/\z and zxcan take any value.
8.3 WHY ANOTHER SYMMETRY NOTAnON
So far, we have employed the Schonflies symmetry notation in our study of group
theory, as is conventional. While we could continue this way into the realm of
crystals, it is very much more helpful to use the HermannMauguin notation. This
notation uses a symbol that defines the positions of the symmetry elements that it
contains, in relation to the x, y and z crystallographic reference axes. As with the
Schonflies notation, the information in the HennannMauguin symbol is always
sufficient to determine all of the symmetry elements of the point group to which it
refers.
A HermannMauguin pointgroup symbol can have up to three positions
(operators) in it that contain symmetry information: from (3.14), it is expected that
there will be information for either one position or three. Certain exceptions arise in
the cubic and trigonal systems. For example, in the trigonal system we find the
pointgroup symbol 3m, where 3 lies in an m plane. We expect three equivalent m
planes under the action of the threefold rotation axis; temporarily, we will call them
m, n andp.
In Figure 8.1, consider the point 1: the threefold rotation takes it to position 2; if it
is now reflected across plane n it is moved to position 3; points 1 and 3 are related
250 Group theory and crystal symmetry [eh.8
now by reflection across the m plane. Thus, in our usual notation for operators, we
write
Similarly,
n3=m
m3 = P
p3 = n
}.
(8.1)
(8.2)
However, planes m, nand p are related by the threefold axis; they belong to one and
the same form of symmetry planes. Thus, only two positions of the symbol are
meaningful; a similar situation arises in the cubic system. We note that point groups
32 (D
3
) and 3m (C
3v
) are trigonal whereas 23 (T) and m3 (Till are cubic.
I
I
I
1
0
+
xl
1
I
I
I 17\+
I V
I 5
I
\
\
m \
\
\
r;.,+ \
10
3
\
Fig 8.1 Partial stereogram of point group C3v (3m): the axes x, y and u (shown by dashed
lines) lie normal to z [C3 (3), indicated by the filled equilateral triangle]; the vertical
reflection planes (shown by full lines) m, n and p are equivalent under C
3
.
We may contrast this situation with that in the orthorhombic system, wherein the
symbol positions relate to the x, y and z axes: under twofold symmetry, none of them
is interconverted.
Table 8.3 indicates the full meanings for the pointgroup symbols in the Hermann
Mauguin notation. It is important to know not only the meaning contained within
each position of the symbol, but also the relative orientation of the different
symmetry elements in the symbol, and the fact that this orientation changes among
the crystal systems according to the nature of the principal axis. Thus, while x and y
relate to separate positions in a symbol for the orthorhombic system, they occupy
one and the same position in a symbol for the tetragonal system, because x and yare
interconverted under the fourfold symmetry along z; then the third position has a
new orientation. The reader may care to sketch stereograms to show these and other
Sec. 8.3] Why another symmetry notation 251
Table 8.3 The HermannMauguin pointgroup notation
System Point groupsa Symbol meaning for each position
1st position 2nd position 3rd position
Triclinic
Monoclinic
b
Orthorhombic
1, I
2
2, m, m
222, mm2,
mmm
All directions
in the crystal
2 and/or 2:
along y
2 and/or 2:
along x
2 and/or 2:
along y
2 and/or 2:
along z
Tetragonal
Cubic
Hexagonal
23, m3
432, 43m,
m3m
6, 6, }
622, 6mm,
6
6m2, mm
m
4 and/or 4
............................ _...__.._..
along
2 and/or 2: 2 and/or 2
z
along at 45
0
to x,
Y
x, y and in
xy plane
2 and/or 2: 3 and/or 3
along x, y at 54.74
0
and z to x, y
and
c
z
4 and/or 4 3 and/or 3 2 and/or 2:
along x, y at 54.74
0
at 45°to
and z to x,
c
y x, y and z
and z
6 and/or 6
..................... _...... .............................................__......
along z 2 and/or 2: 2 and/or 2:
along x, y .I. x, y and
and u u, and in
xyu plane
Trigonal
(Hexagonal
axes)
3 and/or 3
along z 2 and/or 2
along x, y
and u
direction.
3 and/or 3 2 and/or 2:
d  d
.. .. .. J!1.!L .
a) means n .I. m, a single position Involving only one
Trigonal 3, 3, 32
(Rhombohedral 3m, 3m
axes)
m
b) With Y unique, m (= 2 along yl Is the plane ZX.
c) Actually, cos
1
( 1IV3 ) , or along the form of directions <111>.
d) The significance of directions (uVWI will be evident shortly.
252 Group theory and crystal symmetry [eh.8
similar relationships. A thorough understanding of Table 8.3 is the key to the
HermannMauguin symmetry notation.
In elaborating the fact that a HermannMauguin symbol always conveys
information about the relative. orientation of the symmetry elements in a point
group symbol, we note, for example, that in point groups mm2 and mmm, following
(3.14), we have
m.rn, = 2
x
;
m.m.m, =1,
because
We have studied point groups and point group symmetry sufficiently for our
purposes in earlier chapters: the only new feature here is the HermannMauguin
notation, and we shall move towards spacegroup theory by considering first the
concept of a lattice. Further reading on point group theory may be found in the
standard literature[l,7,8l.
8.4 WHAT IS A LATTICE
The geometrical basis of every crystal is its lattice. A lattice may be defined as an
infinite, regular array of(mathematical) points in space such that any point has the
same environment as every other point. The definition applies in one, two and three
dimensions, and the distribution oflattices in space is given below:
Dimensionality
1
2
3
Number of lattices
1
5
14
Lattice descriptor
Row
Net
Bravais
Our particular interest is in the Bravais lattices, with respect to which crystal
structures are built up. Each Bravais lattice may be specified by three noncoplanar
vectors a, b and c, parallel to the x, y and z axes, respectively. The vectors form a
righthanded set (see Section 2.3), and the interaxial angles are denoted a. (y'z), 13
(Z'x) and y(X'y), and may not be always 90°.
Any lattice point may be chosen as an origin, and the vector r uvw to any other point
is given by
r
uvw
== Ua+ Vb+ We (8.3)
where U, Vand Ware positive or negative integers or zero, and may be regarded as
the coordinates of the lattice point; [UVW] defines a direction in the lattice, and
<UVW> a form of such directions.
EXAMPLE 8.1. We calculate (a) the magnitude of the direction [12 3 J, and (b) the angle e
between [123] and the y axis in a monoclinic lattice for which a =0.15, b =0.20, c =0.25
nm, and 13 = 1lO°.
(a) r _ =r _. r _ = (a + 2b  3c}(a + 2b  3c) =a
2
+ 4b
2
+ 9c
2

123 123 123
2a(3c)cos(llOO) =0.449 nm.
Sec. 8.4) What is a lattice 253
(b) They axis is the direction[010]. cos(e) =(a +2b  3c)o(b)/(br _) =
123
2b
21br
_ = 2blr _; hence, e = 27.0°.
123 123
The most general lattice is shown in Figure 8.2: aligning rows of points of spacing
a regularly at another spacing b builds up nets with repeats a and b. When these
nets are stacked regularly at a third spacing c, a Bravais lattice is obtained. We note
that the framework is not the lattice: the lattice is the set of points points, the
framework being merely a geometrical convenience for us.
8.4.1 Defining and choosing unit cells
It would be inconvenient to have to draw a large array of points, such as in Figure
8.2, each time we discuss a lattice. It is useful, therefore, to introduce the concept of
a unit cell. In Figure 8.2, the vectors a, band c outline a triclinic parallelepipedon
which may be taken as representative of the infinite lattice: it generates the lattice by
repeated translation in three dimensions. It has associated with it one lattice point
per unit volume, and is known as a primitive (P) unit cell. Clearly, we can choose a
unit cell in an infinity of different ways. The crystallographic convention is that a, b
and c are chosen parallel to important symmetry directions in the lattice, and
secondarily that the resulting parallelepipedon has a minimum volume. In the
triclinic lattice, there is no symmetry other than a centre of symmetry 1; the
magnitudes a, band c may all differ and the angles between them need have no
y a X i ~
Fig. 8.2 Rows (a) aligned to form nets (a.b); the nets are stacked at a spacing c to form a
Bravaislattice (a.b,c),
special value, such as 90° or 120°, which might imply a higher symmetry for a
lattice.
We need to make a further important point about the unit cell. On the one hand, if
we are considering a lattice, then the unit cell will be centrosymmetric, and each
lattice point site will have the highest pointgroup symmetry of the given system, 1
in the case of othe triclinic system, where the conditions a j:. b j:. c, ex j:. /3 j:. y j:. 90°
254 Group theory and crystal symmetry [Ch.8
or 120° will hold normally. On the other hand, if we are considering a chemical
structure belonging to the tricIinic system, the symmetry may be less than 1. We
shall, therefore, find the term lattice unit cell helpful when discussing the unit cell
of a lattice, and structure unit cell useful when discussing a structure, that is, a
lattice unit cell with contents, and just unit cell when the distinction is either
obvious or immaterial.
The crystallographic choice of unit cell leads to some unit cells being centred,
with more than one lattice point per unit volume. The unit cells of the Bravais
lattices are illustrated in Figure 8.3.
When a lattice possesses symmetry greater than 1 at each point, the vectors a, b
and c may be specialized in a nontrivial manner. For example, if a twofold
symmetry axis passes through each point in the same orientation, then the symmetry
114)
1131
JWJa
I9L
(4) (5) (61 (7)
c c
Fig. 8.3 Unit cells of the 14 Bravais lattices; interaxial angles are 90° unless indicated
otherwise by a numerical value or a symbol: (1) triclinic P; (2) monoclinic P; (3) monoclinic
C; (4) orthorhombic P; (5) orthorhombic C; (6) orthorhombic I; (7) orthorhombic F; (8)
tetragonal P; (9) tetragonal I; (10) cubic P; (II) cubic I; (12) cubic F; (13) hexagonal P; (14)
trigonal R (P). Note that (13) shows a total of three P unit cells: a hexagonal prism of lattice
points without the central basal points is not a lattice. Why? [Reproduced with permission
from Structure Determination by Xray Crystallography by M.F.C. Ladd and R.A. Palmer,
3rd Edition, Plenum Press, 1994.]
Sec. 8.4] What is a lattice 255
at each point is 21m: the vectors a, band c may be selected such that a "* b "* c, with
a. =y = 90° and "* 90°, 120°. The choice of yas the direction of the unique two
fold axis is a crystallographic convention. In group theory, it is more common to
label the twofold axis in 21m (C
2h
) as z. Figure 8.4 is a stereoview of eight adjacent P
unit cells in a monoclinic lattice; it is evident that each lattice point at the comer of
a unit cell is shared equally by eight adjacent such unit cells.
Table 8.4 The fourteen Bravais lattices
System Unit cell/s Axial relationships
in the uni t ce11
Point
symmetry
Triclinic
Monoclinic
P
P, C
a "* b "* C
IX "* (3 "* a "* 90°
or 120°
a "* b "* C
IX = a = 90°, (3 "* 90°
or 120°
I
2
m
Orthorhombic P, C, I, F a
"*
b
"* c
mmm ( D
2h
)
IX (3
= a =
90°
Tetragonal P, I b
4
( D4h
)
a
= "* c
mm
90°
m
IX
=
(3
= a
Cubic P, I, F a
=
b = c m3m ( Oh)
IX (3
a
90°
b
6
( D
6h
)
a =
"*
c mm
Hexagonal P
(3 90° 120°
m
IX ,
a
•
D
3d
)
Trigonal R (P)
a = b
=
c 3m
IX
=
(3
= a
"* 90°
axes
and 120°
<
•
When referred to hexagonal axes, the trigonal system has

a hexagonaltype unit ce I I , but the symmetry remains sm.
256 Group theory aud crystal symmetry [Ch.8
Fig 8.4 Stereoview of eightP unit cellsof a monoclinic lattice.
In Table 8.4, we summarize the Bravais lattices in terms of systems, conventional
lattice unit cells and their axial relationships, and symmetries at each lattice point.
If we are considering a lattice unit cell, the sign should be read as 'is not equal to':
if, for example, we make c equal to a (and b) in a tetragonal lattice, then it is no
longer tetragonal, but cubic. However, if we are considering a structure, it is quite
possible for a tetragonal structure to possess a unit cell in which c = a (and b) within
the limits ofexperimental error. It is still tetragonal: the symmetry is determined by
the arrangement of the contents in the structure unit cell. Thus, when we use the
axial relationships in Table 8.4 in the context of a structure unit cell, we read the
sign :1= as 'not constrained by symmetryto equal'; in the context of a lattice unit cell,
however, ':1=' has its implied meaning.
8.4.2 Why only fourteen Bravais lattices
In a Bravais lattice the environment of each point is identical: a vector, defined
between two lattice points, placed at any given point, will always terminate on
another lattice point. The lattice may be represented by an appropriately chosen unit
cell: however the unit cell may be selected, the lattice itself remains invariant.
From Figure 8.3 and Table 8.4, we see that the lattice unit cells other than P
possess lattice points at centring positions, as well as at the corners of each unit cell.
It is conventional to work with fractional coordinates, so that the results are
independent of any particular unit cell size. Thus, in Figure 8.3(3) the centring
point at a/2, b/2, 0 becomes 1/2, 1/2, 0 in fractional coordinates. The complete list
of coordinates for the unique lattice points in each unit cell type is listed below; the
notation C implies centring on the C face, that containing the a and b unit cell
vectors; I is a body centred and F an all face(A, B and C)centred unit cell:
Unit cell
P,R
C
I
F
Coordinates unique to the unit cell
0,0,0
0, 0, 0; Y2, Y2, 0,
0, 0, 0; Y2, Y2, Y2
0, 0, 0; 0, Y2, Y2; Y2, 0, Y2; Y2, Y2, 0
Sec. 8.4] What is a lattice 257
Consider the tetragonal system. It has lattices represented by P and 1 unit cells,
Figures 8.5 and 8.6, but no others apparently. Suppose we try other centring modes
in a tetragonal P unit cell. Figure 8.7 shows two adjacent Ccentred tetragonal unit
cells. We can outline a unit cell of smaller volume, as shown, which still satisfies
the requirements of a tetragonal unit cell (see Table 8.4). Hence, C and P tetragonal
lattice unit cells are equivalent. If we centre just the A faces the tetragonal symmetry
is lost: if we centre also the B faces the tetragonal symmetry is apparently restored.
However, the (A + B)centred unit cell does not constitute a lattice: each point does
not have the same environment as every other point, Figure 8.8. We can restore
truth to the lattice by centring the C faces as well, to give an F tetragonal lattice unit
cell. Figure 8.9 shows that we can now select a tetragonal 1 unit cell of smaller
volume. Thus, we have only the two tetragonal lattices P and 1. We note en passant
that it is common to refer to a lattice by the symbol of its representative unit cell.
This terminology is, strictly, a misuse of the term lattice, but it may be employed
with this understanding. It may be asked whether or no the tetragonal J Iattice can
be represented by a P unit cell. It can: and we shall consider this point shortly. The
I
I
V
I
/
I
I
V
"""'l
Fig 8.5 Stereoview of a tetragonal P unit cell, z vertical.
I
I
•
V
I
I
/
•
I
V
Fig. 8.6 Stereoview of a tetragonal I unit cell.
258
Group theory and crystal symmetry
[Ch.8
Fig. 8.7 Adjacent tetragonal C unit cells; a P cell is outlined.
P2
r__
Q
Fig. 8.8 'Tetragonal' (A + B)centred unit cell. It is not a lattice: identical vectors PIP; and
P2P ~ do not both start from and terminate at lattice points: their envirorunents differ.
Sec. 8.4] What is a lattice 259
Fig 8.9 Tetragonal Funit cell: a smaller tetragonal I unit cell can now be outlined, as shown.
reason that the conventional unit cell for this lattice is I lies in the definition of unit
cell, that we choose the unit cell edges parallel to the principal symmetry directions
in the lattice.
By these arguments, we can demonstrate that there are only fourteen lattices
within the seven crystal systems. After a test centring of a P unit cell, we ask the
following questions, in order:
1. Does the centred unit cell represent a lattice?
2. If so, is its symmetry different from that of the P unit cell?
3. If not, is the lattice different from the lattice or lattices already determined for
the given system, and has the lattice unit cell been chosen appropriately?
We considered these questions implicity in the discussion of the tetragonal lattices.
The numbers of lattice points associated with the different types of unit cells are as
follows:
Unit cell type P (R) elF
Lattice points I 2 2 4
We derived an expression for the volume of a general parallelepipedon in Section
2.5.2. We note here that, within one and the same lattice, the ratio of the volumes of
any two chosen unit cells is equal to the ratio of the corresponding numbers of the
unique lattice points that they contain.
EXAMPLE 8.2. A facecentred cubic lattice unit cell has a side ac. A primitive
rhombohedral unit cell may be defined within the same lattice by the transformation
aR = Y.bc + Y.cc; bR = Y.ac + Y.cc; CR = 'hac + Y.bc.
We show that its volume is an appropriate fraction of that of the cubic unit cell.
V
c
= a
c
3
• The side aRof the rhombohedron is given by
aR = [(Y.b
c
+ Y.cc)o(Y.bc + Y.cc)]Y. = ad2
The angle a of the rhombohedron is given by (see Section 2.5.2)
cos(a) = (Y.bc + Y.cc )(Y.ac + Y.cc )/(2a
2
) = 1/2, so that a = 60°.
260 Group theory and crystal symmetry [eh.8
Hence, V
R
= a ~ [1  3cos\600) + 2cos
3(600)]I/2
= a ~ 1'12 = a
c
/4, so that VdV
R
= 4, which
is the ratio of the numbers oflattice points in the two unit cells.
8.4.3 Lattice rotational symmetries are 1, 2, 3, 4 and 6
We have remarked earlier that the symmetry of crystals is restricted to the rotational
degrees 1, 2, 3, 4 and 6, and symmetry compatible with them. Molecules with other
rotational symmetry, 5, 7 or 8 for example, are known, but in the solid state they
crystallize in one of the fourteen Bravais lattices. The reason for the restriction on
crystal symmetry can be appreciated from the following argument, based on the
properties of a lattice.
In Figure 8.10, let A and B represent two adjacent lattice points, of spacing t, in
any row of a threedimensional lattice. An nfold rotation axis is imagined to act at
each point and to lie normal to the plane of the diagram. An anticlockwise rotation
<!> about A maps B on to B', and a clockwise rotation of <!> about B maps A on to A'.
Lines AB' and BA' are produced to meet in Q. Since triangles ABQ and A'B'Q are
similar, A'B' is parallel to AB. From the property of lattices, A' B' = Jt, where J is an
integer.
Lines A'S and B'T are drawn perpendicular to AB, as shown. Hence,
A'B' = ST = AB  (AT+ BS),
or
Jt = t  2t cos(<!»,
whence
cos(~ ) =(l .1)/2 =M/2,
T
Q
A
1\
I \
I \
I \
\
\
\
\
\
A·
s B
Fig. 8.10 The rotational symmetry in crystals: the permissible values of <I> are 0° or 360° (1
fold rotation), 180° (2fold), 120° (3fold), 90° (4fold) and 60° (6fold).
where M is another integer. Since 1 S cos(<!» S 1, it follows that the only
admissible values of Mare 0, ±l, ± 2, which give rise to the rotational degrees 1, 2,
3,4 and 6.
Sec. 8.4] What is a lattice 261
8.4.4 Translation unit eells
All Bravais lattices may be represented by primitive unit cells. In seven cases, they
are the P (or R) unit cells in Figure 8.3. For the others, transformations may be set
up in such a way that the transformed (primed) vectors form a righthanded set and
obey the desired condition that the unit cell volume is a minimum.
Many metals crystallize with cubic structures based on I or F cubic lattices. They
may be transformed to P lattices as follows:
Cubic I: a' = al2 + b/2 + e/2,
b' = al2  b/2 + e/2,
c' = al2 + b/2  e/2.
Cubic F: a' b/2 + e/2,
b' = al2 + e/2,
e' = al2 + b/2.
In each case here, the primitive unit cell is a rhombohedron, with an angle 0. of COSI
(1/3) or 60° for I or F, respectively. If considered in isolation, the symmetry of the
rhombohedral unit cell is 3 m (D
3d
) . Of course, the lattice which the unit cell
represents still has the symmetry m3m in each case; 3 III is a subgroup of m3m. The
cubic symmetry is implicit in the special values given above for the angle 0.: a
general rhombohedral lattice unit cell may have any value but, by convention, 0. is
chosen normally to be less than 120°. If 0. takes on one of the special values of COSI
(1/3) or 60°, the lattice unit cell is really of cubic symmetry. The transformations F
~ P are illustrated by Figure 8.11.
Similar transformations of unit cells can be carried out for all centred cells!", and
further notes on unit cells have been presented elsewhere
l42J
. The use of the term
translation unit cells serves to encompass the totality of primitive lattice unit cells,
both Bravais P and those obtained by transformations of the centred cells. The
important point is that both the conventional lattice unit cells and the translation
unit cells generate the fourteen Bravais lattices by threedimensional facetoface
stacking. The translation unit cell is important in the application of group theory to
the solid state.
Fig. 8.11 Transformation F ~ P in a cubic lattice, origin 0; the volume ratio VC/VR has
been deduced in Example 8.2,
262 Group theory and crystal symmetry [Ch.8
8.4.5 WignerSeitz cells
Consider the I unit cell of a cubic lattice, together with the bodycentring points in
the adjacent six similar unit cells of that lattice. Let planes be drawn perpendicular
to and bisecting the lines from the central point to the fourteen points determined,
and allowed to form mutual intersections. The resulting closed figure is a Wigner
Seitz cell and, in this case, is a combination of the cube and octahedron forms,
Figure 8.12. For a cube of side a, the perpendicular distances to the cube and
octahedron faces in the WignerSeitz cell are a/2 and a"J3/4, respectively, so that the
octahedron faces are of the larger area. No other bisecting planes that could be
drawn would intersect the closed polyhedron.
There are twentyfour WignerSeitz cells, more than the Bravais lattices because,
in systems other than the cubic, they depend also upon the axial ratios cia and bla.
A WignerSeitz cell has several properties that are of importance in solidstate
chemistry:
1. In isolation, it has the point group of the crystal system from which it was
derived. Thus, in Figure 8.12 the WignerSeitz cell has the point group m3m
(Oh), whereas the rhombohedron in Figure 8.11 belongs to point group 3 m
(D
3d
) ;
2. It contains one lattice point, so that it is a Ptype of cell;
3. It generates its Bravais lattice by threedimensional facetoface stacking;
Fig. 8.12 WignerSeitz cell obtained tram a bodycentred cubic lattice; no other bisecting
planes can be drawn that lie within this cell. The faces are parallel to the <100> and <111>
forms.
4. All positions within it are closer to the central lattice point than is the next
nearest lattice point;
5. When considered in reciprocal space (k space) it constitutes a first Brillouin
zone.
It should be noted that, except for three particular cases, a WignerSeitz cell cannot
be specified by three noncoplanar vectors along the symmetry directions of the cell.
It is preferable to use the term WignerSeitz cell in this context, rather than Wigner
Seitz unit cell. Further discussions of WignerSeitz cells may be found in the
literature'V?". The use of the several terms lattice unit cell, structure unit cell,
translation unit cell and WignerSeitz cell permits an unambiguous description of
each type of parallelepipedon in common use in chemistry and crystallography.
Sec. 8.5] Translation groups 263
8.5 TRANSLATION GROUPS
We referred briefly to the translation group in Section 3.2.3. The onedimensional
lattice, or row, is an example of a translation group. The row of spacing a that is
part of Figure 8.2 is a onedimensional translation group T
1
that may be written as
follows:
T
1
{oo, ... , ua, ..., 2a, a, 0, a, 2a, ..., ua, ..., oo},
where u is an integer. It possesses all the necessary properties of a group, the zero
term acting as the identity operator. Thus, we find the relationships, under the law
of vector addition
ua + u'a = (u + u')a,
ua + 0 = ua,
ua + (ua) = 0,
where u' is also an integer; ua is the inverse of ua. In three dimensions, the
periodicity conferred by the translations a, band e would appear in the group,
which we can signify as TJ. Whether in one, two or three dimensions, the
translations of ua and/or vh and/or we (u, v, w integral or zero) leave the lattice
invariant.
We may associate the threedimensional basic translations of a Bravais lattice
with three operators A, Band C, such that
Ar
Br
Cr
=
=
=
r + a
r + b
r + c
}.
(8.4)
where r is any vector, and a, band e are the lattice unit cell vectors. Thus,
A"BVC"r = r + ua + vb + we
Equally, we could write
BVe"'A" = A"BVe'"
(8.5)
(8.6)
which shows that the products A"BVe"', under vector addition, form an infinite,
Abelian group, the translation group for the lattice:
(8.7)
where 1 is the HermannMauguin equivalent of the Schonflies E.
We can extend this argument to take account of centred unit cells. For example, a
bodycentred unit cell has unique points at the origin and at \12, \12, Y2, so that the
translation group may be written
T3.I = All2BJl2ell2 T
J
(8.8)
Translation groups are not subject to matrix operations, but (8.5) may be recast in
the form
(8.9)
264 Group theory and crystal symmetry rcn.s
where the Dmatrices represent the symmetry operators A, Band C, and x, y and z
are the fractional coordinate components of a vector r along a, band c, respectively.
If we place an atom, or a group of atoms of point group 6 at the end of a vector r
and operate on it by the translation group T
3
, then T
3
6 r leads to a space group: the
symmetry motif at the position vector r is repeated in an identical orientation at or
around each point of the lattice. A number of space groups, but not all of them, can
be produced in this way, as we shall see.
8.6 SPACE GROUPS
A space group may be defined as a set of symmetry operations the action of which
maps a threedimensional array of atoms on to itself, and so leads to the
indistinguishability of the array after the operation, with respect to its initial
condition.
We have shown that we can represent a pointgroup symmetry operation by a
matrix. Thus, for a fourfold rotation R about the z axis of an orthogonal set of axes,
we have
1
a
a
R r r'
(8.10)
We could choose to write the symmetry operator R more fully as
1
a
a
R t
(8.11)
where t is a translation vector. By definition, t is identically zero for all point
groups, but in space groups it may have nonzero components. Thus, we may write a
symmetry operation generally as
Rr +t = r':
the lefthand side is often expressed conveniently by the Seitz operator; thus,
Rr +t = {Rlt}r

where R may be a rotation or rotoinversion (including 1 and m) operator.
The Seitz operators obeythe following relations.
1. The product {R
2It2}
{R
1ItJJ
is {R
2R
jl(R
2t
j + t2)}:
for if {R
11tJJr
= r', then
{R2It2} {Rdtj }r = {R2It2}r' = R
2r'
+ t2
= R
2(R1r
+ t
1
) + t
2
= (R
2R
j)r + R
2t
j + t2
= {R
2R11(R2t1
+ t
2)}r.
(8.12)
(8.13)
Sec. 8.6] Space groups 265
Thus, if R
I
and R
2
are members of a space group, their product R
2RI
(or R
IR2
) is
also a member of the same group; it follows that the associative law is obeyed by
Seitz operators.
2. The inverse {Rltr
l
is {RIIRlt}:
for the product rule gives
{Rltrl{RIIRlt} = RRIIRlt + (Rlt) = {ljO},
where {110} is the Seitz identity operator.
If any or all of the components of the translation vector are integral, then we are
involved with translations of an integral number of lattice unit cells. However, in
applying the Seitz operator to the formation of space groups, it is found that
translation vectors within the unit cell arise, too. This situation allows for a
separation of space groups into two types, symmorphic space groups (also known as
point space groups) and nonsymmorphic space groups.
8.6.1 Symmorphic space groups
There are 230 space groups in all. We shall not consider here the black/white
groups, or the colour symmetry groups, one of which appears on the book jacket.
Attractive discussions of these topics are given in the literature[47
49
l.
A symmorphic space group is generated by the action of a Bravais lattice on a
motif of pointgroup symmetry. Although specified entirely in these terms,
translations arise in those symmorphic space groups that are based on centred unit
cells. If we take the point groups of Table 8.3 together with the Bravais lattices in
Table 8.4, we generate 66 symmorphic space groups (including both trigonal Rand
P). However, to them, we need to add the following space groups.
Orthorhombic: Amm2. Although an orthorhombic A lattice unit cell is equivalent to
a C, by transformation of axes, the space group Amm2 is not equivalent to Cmm2; in
the latter space group the centred unitcell face is normal to the unique, twofold (z)
axis.
  
Tetragonal: P 4 m2, 14m2. They differ from P 4 2m and 142m because of a change
in the orientation of the pointgroup motif with respect to the Bravais lattice unit
cell: in P 4 2m, for example, the m planes are normal to the directions [110] and
 
[110], whereas in P 4 m2 they are normal to [100] and [010].
 
Trigonal: P312, P31m, P 3 1m (different fromP321, P3ml and P 3 ml).
 
Hexagonal: P 6 2m (different from P 6 m2).
There is, thus, a total of 73 symmorphic space groups; they all have at least one site
of symmetry which is that of the point group of the space group. Fuller discussions
of these and other space groups are given in the standard literature(l,7,46
J
•
Monoclinic symmorphic space groups
We consider first the monoclinic space groups Pm and Cm. The choice of origin is
arbitrary, but normally it is taken on a symmetry element. Thus, the m plane in
these two groups is specified as the plane (xqz), where q is chosen as zero. Applying
the Seitz operator, we have
266 Group theory and crystal symmetry [Ch. 8
where D(m) is the matrix representing an m plane operator at (x, 0, z). In space
groups, it is common terminology to place the negative sign above the coordinate to
which it applies, unless it is combined with a translation. The coordinates generated
by the spacegroup symmetry are termed general equivalent positions (or
equipoints); they occupy sites of identity symmetry, and are equal in number to the
order h of the point group of the space group.
We consider next the space group Cm. We may always regard a centred space
group as the corresponding primitive group plus the translations associated with the
centred unit cell, as shown by (8.8). Thus, we obtain coordinates as follows:

x, y, z; x, y , z; Yz + x, Yz +y, z; Yz + x, Yz  y, z.
It is useful to represent space groups by drawings that show the symmetry elements
and the general equivalent positions. Figure 8.13a illustrates Pm: the drawings are
normally displayed on the :\y plane, with +x running from top to bottom, +y running
from left to right and + z directed upwards, towards the observer, the three axes
forming the conventional righthanded set. The heavy lines indicate the positions of
the m planes, normal to y, in the space group. The halving symmetry elements are to
be found in all space groups: in this case it arises, in a unit cell, from the
relationship between pairs of points like x, y, z and x, I  y, z.
As well as the coordinates of the general equivalent positions, there are two sets of
special equivalent positions, on nontranslational symmetry elements, m planes in
this case; they form a subset of the general equivalent positions under the symmetry
Pm.
If we compare now the diagram for Cm, Figure 8.13b, we note that there is only
one set of special equivalent positions, because both m planes must be occupied to
conform to the symmetry Cm. A postulated second set, by analogy with Pm, might
be x, Yz, z and Y2 + x, 1, z. However, these coordinates represent another pair of sites
on the same m planes, and do not constitute another set of special equivalent
positions: we note that pairs of fractional coordinates x, y, z and x ± i, Y ± j, Z ± k,
where i, j and k are integers, are crystallographically equivalent under any space
group symmetry.
Sec. 8.6] Space groups
267
l!l+ 0+
I
®+ 0+
Ca)
l!l+ 0+ ®+ 0+
Origin on m
2 x, y, z; x, y, z.
1
m x,
2'
z.
m x, 0, z.
0+ I I
®
+
I
I
I ®+
0+ :
I I
Cb)
l!l+ 0+ l!l+ 0+
Origin on m
4 1 x, y, z; x, y, z;
1 1 1
.!.
 + x,  + y, z;  + x,  y, Z.
2 2 2 2
1 1
2 m x, 0, z; 2 + x, 2' z.
Fig 8.13 Synunetry elements and coordinates of general and special equivalent positions in
space groups (a) Pm, and (b) em.
A second feature in On, indicated by the dashed lines, is the presence of glideplane
symmetry. The glide planes interleave the 111 planes, and relate pairs of points such
as
x, y, z; 12 + x, 12  y. z.
The operation here consists of reflection across the plane at (x, 1;4, z) plus a
translation of Y2 along a, or x, (for an aglide plane), the two movements
constituting the one glidesymmetry operation; we shall say more about glideplane
symmetry shortly. We may note that the unit cell of a space group is a structure unit
cell; the lattice unit cell symmetry in the monoclinic system is always P2lm or C21m.
We look now at space groups P2 and C2. The Seitz operator leads to the following
relation for P2, with 2 taken along y, by convention: the translation vector t is zero.
{D(2)IO}r =
a
1
a
(8.14)
268
GrOUI) theory and crystal symmetry [eh.8
0
0
0+ 0+
0 0
Origin on 2
e x,y,z; i,y,z.
d 2 !, y, !.
2 !oy, O.
b 2 0, y, !.
a 2 O,y,O.
Fig 8.14 Symmetry elements and coordinates of general and special equivalent positions in
space group Pl:
0
0
Figure 8.14 shows space group P2. There are four sets of special equivalent
positions, because there are also twofold axes, unique to the unit cell, at (±)Y2 along
c. The nature of the m symmetry element precludes this situation for Pm.
If we Ccentre P2, we obtain space group C2, Figure 8.15: alternatively, we could
apply a pattern motif directly to a monoclinic C lattice. In centred groups, it is
conventional to list the coordinates for the corresponding primitive group and head
that list with the translations to be applied to that list, namely 0, 0, 1 and Y2, Y2, °for
a Ccentred cell. As in P2 there are twofold axes at ±Y2 along c, and the number of
sets of special positions is half of that in P2.
We encounter now a new feature, that of the screw rotation axis, or just screw
axis, symbolized by the halfarrow ,. In this example, it relates pairs of points such
x, y, z and Y2  x, Y2 + y, z. The operation consists of a twofold rotation about b
followed by a translation of Y2 along b, again a single symmetry operation overall.
We pause in our discussion of space groups to examine glide planes and screw axes
in more detail.
0+
0+
0
0+
0
0
Origin on 2
4
(0,0,0; U,O)+
X.y,z; i,y,i.
2 b 2 O.y,!.
2 a 2 O,y,o.
Fig. 8.15 Synunetry elements and coordinates of general and special equivalent positions in
space group C2.
Sec. 8.6] Space groups
269
Fig. 8.16 Illustration of glideplane synunetry. [Reproduced with permission fromSymmetry
Aspects ofMiC, Escher's Periodic Drawings, byC.H. MacGillavry, Oosthoek, 1965.]
Glide planes and screw axes
A glideplane symmetry is illustrated by Figure 8.16. We may identify a structure
unit cell by the tips of the noses of four adjacent men in identical orientation.
Within this unit cell there is another similar man, but looking the other way, the
mirror image: it is also translated by \12 along a, and so is related by glideplane
symmetry to the man at any corner of the cell.
Glide planes are named according to the direction of their translation. Table 8.5
indicates the glide planes that occur among the 230 space groups. We indicate their
orientation by notation such as (x, q, z), which means the xz plane intercepting the y
axis at a fractional value q. The orientations given in Table 8.5 refer to the standard
settings of these space groups!". For other settings of the axes with respect to the
symmetry elements, appropriate adjustments may be made.
An example of screwaxis symmetry is shown in Figure 8.17. A screw axis may be
generalized as nip: the operation is an anticlockwise rotation about the axis by
(360In)0 plus a translation of pin of the repeat distance along the axis. In Figure
8.17, a 6
1
screw axis is shown: indistingushability exists for a rotation of 60° plus a
translation of 1/6 along c. For p = n, nip equates to a pure rotation plus the
translation repeat in the direction of the axis. Table 8.6 lists the screw axes for the
230 space groups; we use the notation [P, q, z] to represent an axis along z, at x = p
andy = q.
Figure 8.18 is another example of a glide plane, an aglide plane. We introduce
here the concept of an asymmetric unit of the structure unit cell, that is, a portion of
the unit cell that produces a crystal when acted upon by the spacegroup symbol.
Thus, the asymmetric unit here is one half of the unit cell, either 0 to 1, 0 to 1/2 and
oto 1, or 0 to 1/2, 0 to I and 0 to I, along a, band c, respectively. The glide plane
takes the flower at point 1 across the plane to point I' transiently, and then
270
Group theory and crystal symmetry
icu s
translates it by 1/2 in the direction of a to point 2. The space group for this pattern
is Pa, which is equivalent to the standard symbol Pc.
Table 8.5 Notation for glide planes
Symbol Orientation Translational component
a 1. paper (x , p, z)
}
II paper (x, y, r)
1/2 along a
b 1. paper (p, y, z)
} II paper (x , y, r)
1/2 along b
c 1. paper (p, y, z)
}
and/or (x , z)
1/2 along c
q,
n 1. paper (p, y, z) 1/2 along b and c
and/or (x , q, z) 1/2 along c and a
1/ paper (x , y, r) 1/2 along a and b
and/or (x , q, z) 1/2 along c and a
and/or (x , x, r) 1/2 along a, band c
d 1. paper (p, y, z) 1/4 along b and c
and/or (x , q, z) 1/4 along c and a
II paper (x , y, r) 1/4 along a and b
and/or (x, x, r) 1/4 along a, band c
Sec. 8.6] Space groups
271
Table 8.6 Notation for screw axes
Symbol Orientation Translational component
2 .L paper [p, q, z) 1/2 along c
1
II paper [p, y, r] 1/2 along b
and/or [x, q, r] 1/2 along a
3 .L paper [p, q, z] 1/3 along c
1
3 .L paper [p, q, z] 2/3 along c
2
4 .L paper [p, q, z] 1/4 along c
1
4 .L paper [p, q, z] 2/4 (1/2) along c
2
4 .L paper [p, q, z] 3/4 along c
3
6 .L paper [p, q, z] 1/6 along c
1
6 .L paper [p, q, z] 2/6 (1/3) along c
2
6 .L paper [p, q, z] 3/6 ( 1/2) along c
3
6 .L paper [p, q, z] 4/6 (2/3) along c
4
6 .L paper [p, q, z] 5/6 along c
5
Fig 8.17 A 6
1
screw axis: the repeat distance in the direction of the axis is c, and the screw
translation is 1/6 along c.
272 Group theory and crystal symmetry [eh.8
o
b
Fig. 8.18 Glideplane symmetry: an a glide plane at (x, 'I., z). The flower at position 1 is
reflected across the plane to position l' transiently, and then translated to position 2; the two
actions constitute a single symmetry operation.
Having discovered glide planes and screw axes, we may ask if there are space
groups that can be built on these symmetry elements, either partially or wholly, that
could not be obtained in the manner discussed so far, a question that leads us into
our next topic.
8.6.2 And nonsymmorphic space groups
If it is necessary to specify a space group by including either a glide plane or a screw
axis element in the symbol, the space group is termed nonsymmorphic; we consider
some space groups of this type.
Monoclinic nonsymmorphic space groups
We introduce two space groups, P2) and P2)/c. For the first of them, we need to
postulate a 2) axis along the line [0, y, 0]. A 2) screw axis along y has a translation
of '12 in that direction, so that the Seitz operator for this symmetry becomes
{2dt(0, '12, O)}r = r';
For convenience, we shall understand the first symbol in the operator to mean the D
matrix for that operator. In extenso, we have
o
1
o
and a diagram for this space group is shown in Figure 8.19. Screw axes, unique to
the unit cell, exist also at ±'12 along a, c and (a ± c), but there are no special
equivalent positions in this space group because there are no positions of
nontranslational symmetry: the occupancy of a special position (of pointgroup
symmetry) implies at least that symmetry for the occupying species.
A space group of frequent occurrence is P2]/c. We associate this space group with
point group 21m (remove the unitcell symbol, and convert translational symmetry
elements to the corresponding elements without translation), so that 2) is parallel to
y, and c is nOIDIal to y. We know also that 21m leads to a centre of symmetry (1 ) at
Sec. 8.6] Space groups
0
0+
Origin on 2,
2 a x,y,z; i,1+y,i.
I
I
273

t (l)
Fig. 8.19 Synunetry elements and general equivalent positions in P2.; there are no special
equivalent positions in this group.
the intersection of 2 and m. It follows that 2
1
combined with c also leads to a centre
of symmetry, but it will not be at their point of intersection. Having chosen 2
1
along
[P, y, r], with the eglide plane at (x, q, z), we may proceed in various ways.
Let us assume initially that p = q = r = O. The matrix for the 2
1
axis has been
considered above, for space group P2
1
• The cglide operation has a translation of 'I:z
along c, and in matrix form it is given by
[ ~  : ~ ] [  ~ :~ ] ·[!]·[!][  ~ :  ~ ] ·[l].
 1
c(X,O,Z 2 (O,y,o t t c: t(2) 1(0,,) t
1 1 2 1
We note first that these matrices lead to a satisfactory representation of space group
P2
1
/c. However, it is conventional, and convenient, for the centre of symmetry to be
at the origin. We can find the position of the centre of symmetry from the product of
the symmetry operations 2
1
and c. In this process, we multiply the symmetry
matrices and add the translation vectors:
[n· [n = [:]  [n
t rc i t r z )
1

so that I lies at 0, '!.t, '!.t. If we place the centre of symmetry at the origin of the unit
cell, it is evident that the c glide must be at (x, 1.4, z) and the 2
1
axis at [0, y, 1.4].
The translation vectors will be changed, and we can adjust the coordinates of the
274
Group theory and crystal symmetry
G o 0
0+
~ + 0
0+
1
0
02  0
tcns
0+
0+
Fig. 8.20 Symmetry elements and general and special equivalent positions in nile; 21 axes
are present also at 3/4 along e.
equivalent positions accordingly. We can always change a coordinate by ±l in a
space group to give a crystallographically equivalent position. Alternatively, we may
use translations of Y2 in either tee) or t(2
1
) . Figure 8.20 illustrates P2
1
1c in the
standard orientation.
If a symmetry axis parallel to y intersects the z axis at the value r, then z ~ 2r  z;
furthermore, if a eglide plane lies normal to the y axis and intersects it at the value
q, then y ~ 2q  y. The latter result is illustrated by Figure 8.21, and similar
procedures can be applied quite generally.
We can achieve the desired orientation of a space group in a onestage process by
means of the following argument, which we illustrate here with P2
1
1c. The centre of
symmetry is displaced from the origin 0, 0, 0 because of the translational
components of the symmetry elements 2
1
and e. Thus, to find the position of the
centre of symmetry we add the translations implied by the symbol, (b/2 + el2), and
halve the result, (b/4 + el4). Hence, to obtain the centre of symmetry at the origin,
the 2
1
axis must be the line [0, y, 1!4], and the e glide the plane (x, \14, z). This
orientation leads directly to the translation vectors as given above already, and this
procedure is often termed the halftranslation rule.
c glide plane normal
to the y axis at y=r
..
o r:r
'12+
(!)
yaxis
y
tx axis
\:)
roy
Fig. 8.21 A symmetry plane cutting an axis y at a position r from the origin means that the
coordinate along that axis, y, changes from y to (2r  y) on operation of that symmetry
element.
Sec. 8.6] Space groups 275
Orthorhombic nonsymmorphic space groups
Orthorhombic space groups are a little more numerous. We have point groups 222,
mm2 and mmm, and lattices P, C, I and F and, in point group mm2, A also. We
should now be able to see what space groups will arise for crystal class 222, and the
diagram of Figure 8.22 indicates them. For instance, C centring introduces half
translations along x and y, so that only C222\ is a new group, different from C222;
C2\22, C2\2\2 and C22\2 are alternative, nonstandard names for C222. We will
consider only P2
12121
in this class.
In this space group, we have to determine three Seitz symbols that relate to
nonintersecting 2\ axes; if any two 2
1
axes intersect, we would obtain P2
122\
or
P22
12},
both of which are equivalent to P2
12 12.
For 2
1
parallel to x, we write the
Seitz operator as
{2
1,xlt(Y2,
Y2, O}r = r
',
or, in matrix notation,
The translation of one half along x is determined by the nature of the symmetry
element parallel to x: we need not have chosen its particular intercept of 114 along y,
but we wish to obtain the standard setting of this space group, with the origin
midway between the three pairs of nonintersecting 2\ screw axes.
For the y direction, a 2
1
axis that does not intersect the first is obtained by setting
it along [0, y, Y4]:
{2
1J'lt(0,
Y2, Y2}r = r'.
I P222
+C
I C222 I I /222 I I
I
F222
I
+ /
I
t
+F
I P2
121
2
1
+C
+ /
I
+F
+ C I C222 I
I P222
1
:
, 1
+ /
I
+F
+C
1P2121
2
d 1/212
1
2
1
I
+/
I
•
+F
Fig. 8.22 Space groups in class 222: in P2
1212
only the 21 axes intersect, whereas in P222\,
21 intersects 2. If any two axes in P212
121
intersect, P21212 is obtained.
276 Group theory and crystal symmetry [Ch.8
Then the third nonintersecting screw axis takes an orientation along the line ['!4, 0,
z]:
{2
1
,zlt(lh, 0, Ih}r = r'"
The coordinates generated by these operations on a point x, y, z lead overall to the
four general equivalent positions shown in Figure 8.23.
0'''
r"
0+ I
• ,',to
i
I "/0
'.
Oi
..
•
i
, 0'2
• 0+ 0'+ '•
Origin halfway between three pairs or nonintersecting screw axes
4 a 1 x,y.z;
Fig. 8.23 Symmetry elements and general equivalent positions in n,21h there are no
special equivalent positions in this group.
We shall examine one space group in the class mmm. The three symmetry plane
operations of the space groups in this class interact to produce a centre of symmetry.
Again, it will be set off from the origin by the total effect of any translations
indicated by the spacegroup symbol. Consider space group Pnma; the following
information is contained in or derivable directly from the symbol, and illustrates the
power of the HermannMauguin notation:
1. Point group mmm: thus, the space group is orthorhombic;
2. Lattice is referred to an orthorhombic P unit cell;
3. nglide plane perpendicular to x, translation Y2 along band c (diagonal);
4. mplane perpendicular to y;
5. aglide plane perpendicular to z, translation Ih along a;
6. 1 offset from the origin by '!4 along a, band c;
7. Full symbol for mmm is
222
, so that there will be 2 or 2] axes normal to the
mmm
symmetry planes.
To proceed, we could write the Seitz symbols: for example, for the nglide plane,
we have
{nlt(O, Y2, Y2} r = r',
and so on. Instead, we could apply the halftranslation rule to show that the nglide
plane is at ('!4, y, z), the III plane at (x, 'I., z), and the aglide plane at (x, y, 114), for 1
to be at the origin.
Sec. 8.6] Space groups
277
Another scheme that we can employ makes use of the sign changes for a point x,
y, z under the symmetry operations of 222, as indicated by Figure 8.24. With
mmm
the aid of this scheme, we can write down the coordinates for space group Pnma.
From the spacegroup symbol, we have the following general orientations for the
symmetry elements, under the condition that I lies at the origin:

I at 0,0,0;
n at (p, y, z); m at (x, q, z); a at (x, y, r);
2p at [x, B, C]; 2
Q
at [A,y, C]; 2
R
at [A', B', z].
The eight general equivalent positions can now be given, as follows:
(1) (2) (3) (4)
X,y,z; 2p  x, '12 +y, '12 + z; x, 2q  y, z; '12 + x, y, 2r  z;
   
x, y, z ; 2p + x, '12  y, '12  z; x, 2q +y,z; '12  x, y, 2r + z.
(5) (6) (7) (8)
m , , ~
JRlmlxl
m 1 y
~ t
 + +
I I
+  +
I ~
11 (0,0,0)
1
1
1
1
1
1
I
I2#J
+  
I
 +    +
2/1y
2/1z
Fig. 8.24 Variation in the signs of the coordinates of the general equivalent positions in
space groups of the mmm class.
Pairs of coordinates such as I, 2 and 4, 7, or I, 3 and 2, 8 are related by the same
symmetry operations. Hence, it follows that p = q = r = 1/4. Furthermore, pairs such
as I, 6 show that P = I, B = C = 1/4; also Q = I, A = C = 0, R = I, A' = 1/4 and B'
= O. Thus, the full symbol of the space group is P ~ ~ ~ , and Figure 8.25
n m a
illustrates this space group. We can always check that we have found the total
number of symmetry elements in a space group by the following simple procedure.
Take any general equivalent position, say x, y, z, and ensure that every other
position on the structure unit cell diagram can be reached by a single operation: for
example, the site x, I + b. z by the translation b; 112 + x, '12  y, Y2  z by the 2
1
axis at
[x, 114, 114], and so on.
Some useful rules
From our study of space groups so far, the following rules emerge that apply to all
space groups (and point groups) in the triclinic, monoclinic and orthorhombic
systems (and a number of others), concerning the signs of the x, y, z coordinates
under symmetry.
278
Group theory and crystal symmetry
'4
:,
0
0
0
0
+0 0
. 
1


''2
0
'",+
''20
0
0',
..,0 0'2
< 
I  1
. 
._. l
0
0
0
0+
+0
0+
[eh.8
8 d 1 x, y. z;
.t, j. r.
4 c m x, t z;
4 b i 0.0.1;
4 a i 0.0.0;
Origin at i
i.!+y,i; !x,y,!+z;
!+x,y,!z.
lx.t!+z;
O.U; \,0.0; 1.1.0.
0.1.0; !.o.!:
Fig. 8.25 Synunetry elements and general and special equivalent positions in Pnma; 21 axes
are present also at 3/4 along c. The symbol ee indicates the n glide, and """1 Yo the a glide at
1/4 (and 3/4) along c; , indicates a 2
1
axis along z.
1: changes the signs of all coordinates.
2 (2
1
) : changes the signs of two coordinates, other than that in the direction of the
symmetry axis.
m (a, b, c, n, d): changes the sign of one coordinate, that in the direction normal to
the symmetry plane.
Tetragonal nonsymmorphic space groups
Tetragonal space groups are more complex than orthorhombic. However, they
introduce new features, and we shall consider just one of them, P4bm. It is related to
point group 4mm and, desirably, 4 is taken along [0, 0, z). We know that in point
group 4mm both forms of m planes intersect in the fourfold axis (see Figure 3.12): it
follows that in P4bm the intersection of the bglide and m planes must be offset from
this axis. Let the b glide be the plane (P, y, z) and m the plane (q, q, z). The Seitz
operator and consequent matrix for the fourfold rotation are:
{410}r = r',
1[:] + [ = [:]
From a second and third, consecutive operations, we generate also the points x, y,

z andy, x, z.
For the bglide operation, we have
{blt(2p, lh, O}r = r',
Sec. 8.6] Space grOUI)S
279
From the other three points obtained so far, we generate 2p +y, \12 + X, z and 2p + x,
Y2  y, z and 2p  y, 1/2  X, z with the b glide.
For the m plane, we write
{mlt(q, q, O}r = r',
From the signs of x, y and z, we see that we have generated this position already, as
2p  y, Y2  x, z: since b4 = m in this group, no new points will be generated by the
m operator. By comparing coefficients, q = 1/2 and p = q/2 = 1/4. The coordinates
for the bglide operation are justified through Figure 8.21, and that for the m
through Problem 8.14. It should be evident that the bglide and the aglide, at (x, II.,
z), operations are equivalent under the symmetry operation 4.
Figure 8.26 shows a drawing for this space group taken from the International
Tables for XRay Crystallography!", which may be taken as the definitive work on
P4bm No 100 P4bm 4mm Tetragonal
C
2
.
4v
()+
+00+
+00+
()+
0+
+0
+0
0+
+0
0+
0+
+0
+0
+00+
+0 0+
+0
Origin on 4
Number or positions.
Wyckof' notation.
aDd poiat symmetry
Coordinates of equivalent posiuons
Ccnditicns limiting
possible reflections
d
1 x,y,z; Ji,y,z; i+x,iY,z; ix,i+Y,z;
y,x,z; y,!I,z; i+Y,i+x,z; iY,ix,z.
General:
hk/: No conditions
Ok/: k2n
hh/: No conditions
4
m x,i+x,z; .f,ix,z; i+x,.f,z; ix,x,z.
Special: as above, plus
no extraconditions
2 b mm i,O,z; O,i,z· }
hkl: h+k2n
2 a 4 0,0,:; M,:·
Fig. 8.26 Synunetry elements and general and special equivalent positions in P4bm.
[Reproduced with permission from International Tables for XRay Crystallography, Volume
I, edited by N.F.M. Henry and K. Lonsdale, Kynoch Press, J965.]
280
G.oUJl theory and crystal symmetry [Ch.8
the 230 space groups and other aspects of crystal symmetry. Other discussions of
space groups may be found in the
Certain features of Figure 8.26 call for mention. The second column is a notation
due to Wyckoff that is used simply to refer collectively to a set of equivalent
positions; we have met columns one, three and four already. The righthand column
lists the conditions that govern Xray reflection from crystals of this space group; it
is not our concern, and has been discussed elsewhere!':".
8.7 APPLICATIONS OF SPACE GROUPS
Inconjunction with Xray analysis, spacegroup data is important to the structure
solving process. We consider some examples here that demonstrate the information
that may become available once the space group of a crystal is known.
Naphthalene
Naphthalene crystallizes in the monoclinic space group P2
1/c.
The unitcell
dimensions are a = 0.866, b = 0.600. c = 0.824 nm. = 122.9°, and the density of
the crystal is 1180 kg m'. Since M, = 128.2. the number Z of molecules in the unit
cell is 1.99, or 2 to the nearest integer. Since there are four general equivalent
positions in space group P2]/c, the molecules lie in special positions of 1 symmetry.
Figure 7.7 (Section 7.5) illustrates the crystal structure of naphthalene; the
asymmetric unit is one quarter of the unit cell and contains one half of a
naphthalene molecule, with the centre of the molecule lying on a site of 1
symmetry.
Biphenyl
Biphenyl also crystallizes in space group P2]/c with two molecules per unit cell.
Again, the molecules lie on centres of symmetry, such as 0, 0, 0 and 0, 1'2, \.1. We
note that the special positions used must be one of the sets of special equivalent
positions that form a subset of the general equivalent positions (see Problem 8.17),
obtained from them. in this case. by the substitution x =y =z = O. It follows that the
molecule of biphenyl is centrosymmetric, and hence of a planar structure. Thus,
conjugation exists throughout the molecule, with a partial doublebond character of
the central CC bond; this bond has a length of is 0.147 nm (see also Figure 6.7).
The molecule is stabilized in this conformation in the crystal by intermolecular
electron overlap: electron diffraction and theoretical studies on the free molecule
show that its minimum energy conformation occurs with the ring planes at
approximately 45° to each other.
Two cubic structures
Sodium chloride Na"cr crystallizes with the cubic space group Fm3m; there are
four formulaentities per unit cell. A selection of the special equivalent positions for
this space group is listed:
Sec. 8.7] Applications of space groups 281
(0, 0, o· 0,
1 1 1
0,
1 1 1
0)

+
,
2' 2' 2' 2' 2' 2'
8 c 43m
1 1 1 3 3 3
4' 4'
4;
4' 4'

4
4 b m3m
1 1 1
2' 2'

2
4 a m3m
0, 0, o.
It is clear that we may choose positions (a) or (b) for the Na+ species. If we choose
(b), then the Cl' species occupy (a). Thus, the structure of sodium chloride is fully
determined, and Figure 8.27 is a stereoview of its unit cell.
Fig 8.27 Stereoviewof the unit cell and environs of the sodiumchloride structure: cr ions
in set (a), Na+ in (b).
Barium titanate BaTi0
3
crystallizes in space group Pm3m with one formulaentity
in the unit cell. The special equivalent positions in this space group include the
following sets:
6 e 4mm x, 0, o· 0, x, o· 0, 0, x· , , ,
x, 0, o· 0, x, o· 0, 0, x. , ,
3 d
4 1
0, o· 0,
1
o· 0,
1
mm 

0, 
m
2'
,
2 '
,
2
3
4
0,
1 1 1 1 1 1
C mm 
_.

0,
  o.
m 2' 2' 2' 2'
2 '
2'
1 b m3m
1 1 1
  
2 '
2'
2
1 a m3m 0, 0, o.
It follows that barium occupies site (a) or (b) in the unit cell; we choose (a); then
titanium lies at (b). For oxygen, we have either (c) or (d). It is not difficult to show,
from standard radii, that with titanium in (b) the oxygen atoms must lie in positions
(c) In BaTi0
3
the unit cell side a =0.398 nm. The relevant ionic radii are[52) Ba
2+
=
0.149,0
2
= 0.125 nm, The half facediagonal of the cube is 0.398lV2 = 0.281 nm,
which is close to the sum of the radii, whereas the sum of 2rB/+ + 2r0
2
 = 0.548 nm,
which is greater than a. Other examples of the use of spacegroup data in structure
determination may be found in the literature'".
282
GrOUJl theory and crystal symmetry [Ch.8
8.8 WHAT IS A FACTOR GROUP
We have discussed the fact that the point group 6 of a space group R has a zero
value for the translation vector t of (8.12). The symmetry operations of R include
the translation group T3 of (8.7) and other operators that may have translational
components. Thus, we have Seitz operators of the form {Ijt.} and t(
refers to translations of the group T3, the a, h, c vectors, and R, and t] refer to the
other j symmetry operations with their translations, such as glideplane and screw
axis operations; both of these Seitz operators lead to infinite arrays of atoms.
If we divide out the operators of T3, we obtain groups of finite order known as
factor groups: thus, the factor group of Pm3m is m3m (Oh), of order 48. The factor
group and the point group of a given space group are isomorphous: there is a oneto
one correspondence between the members of the two groups (see also Section 3.3.2).
Consider the structure of trimethylammonium chloride (CH3)3NHCl, which
in space group P2]/m with two molecules per unit cell; the groups
H /N<H lie in the m planes. In the factorgroup model, we ignore the
translational symmetry T
3,
so that the relationships between the symmetry operators
of space group P2}/mand point group 21m (C
2h
) are as follows:
Point group
Space group
21m (e
2h
)
P2]/m
1 (E)
1
Hence, a character table for Putm may be derived from the onetoone
correspondence with 21m; this table is given in Appendix 11, under the heading C
2h
.
Thus, there is no reference to the translations implied by the symbol P.
In centred space groups, it is desirable to transform to a primitivetype unit cell. A
primitive translation unit cell may be obtained by an appropriate transformation,
such as C + P, in extenso as
b
c c ) [ .!. C 2
1
2
a
1
2
1
2
a
b
p
or by defining a WignerSeitz cell (see Section 4.4.4ft).
8.8.1 Simple factorgroup analysis of irontff) sulfide
We consider an analysis of the binary intermetallic compound iron(II) sulfide FeS. It
crystallizes in space group P6
3
lnc with two formulaentities in the unit cell. Each Fe
atom is cooordinated by six sulfur atoms in a slightly distorted octahedron, and each
S atom is coordinated by six iron atoms at the corners of a trigonal prism. Some of
the special equivalent positions in P6
3
mc are listed below:
6 c m x, x, z; x, 2x, z' 2x, x, z; ,
1
 1
1
2x,
 + z; 2x, x,  + z.
x, x,  + z' X,
2
,
2
2
1 2 2 1 1
2 b 3m z'
3'
+ z.
3' 3'
,
3' 2
0, 0,
1
+
2 a 3m 0, 0, z;
z.
2
Sec. 8.8] What is a factor group 283
It is evident that Wyckoff positions (a) and (b) are occupied, and we may place Fe in
(a) and S in (b).
The factor group is 6mm (C
6v
) , and we can determine r
3n
on the basis of unshifted
atoms (UA), as in working with a point group.
UA(Fe)
r.,
1 26
2 0
6 0
23
2
o
2 2m
x
o 2
o 2
(The symmetryclass multipliers are given here in italics).
A similar analysis applies to the sulfur atoms, so that overall
r
3n
= 24
1
+ 2B
I
+ 2E
I
+ 2E
2
The overall dimensionality of r 3n is twelve, which is correct for the number of atoms
present in the P unit cell. We observe here one reason for choosing a primitivetype
cell in studying vibrations in the solid state: it involves handling half the number of
vibrations, as compared with the simplest of centred unit cells.
The scattering of incident radiation by atoms in a crystal, often termed lattice
vibrations, is of two types: that in which the atoms in each unit cell move in phase
with one another produces acoustic phonons, whereas that in which the atoms
vibrate with respect to one another leads to optic phonons. We can liken the acoustic
modes to translations and rotations in a freemolecule situation, so that it is the optic
phonons that give rise to infrared and Raman spectra in solids.
In our example the acoustic modes belong to the translations x, y and z which
span a, and E
I
in 6mm. Hence, we find
r
vib
= Al +2B
I
+E
I
+2E
2
The number of vibrational degrees of freedom is nine, or 3n  3 based on the P unit
cell, since rotation is absent in the solid state, except in certain special cases. For
infrared activity, we need the results of the direct products
A@[E
A1]@A(2B.E.2E).
1 1 1 1 2
1
so that infrared activity arises for Al and E
I
. For Raman activity we need
A
,
@ [ ;:J @ A, (2B
"
£" 2£).
2
so that Raman activity arises for AI, E
I
and 2E
2
, with coincidence in Al and E
I
;
P63fflcis a noncentrosymmetric space group.
We can arrive at this result by a symmetry ascent technique. The Fe and S atoms
lie on sites of symmetry 3m (C
3v
) , and the translational movements for that group
span Al (z) and E (x, y). The ascent of symmetry to 6mm (C
6v
) may be determined
from a 6mm correlation table. We find (see AIl.l, Appendix All):
284
Group theory and crystal symmetry [Ch.8
6mm (C6v)
A
1
B
1
E
1
E
2
A
1
A
1
E
E
The vibrations of an atom may be resolved along directions x, y and z. Thus, two
iron atoms on 3m sites in irreducible representations AI + E ascend to 6mm as A] +
B] + E] + E
z,
so that for both species together, we obtain f
3n
= 2A
1
+ 2B] + 2E
1
+
2E
z
and I'vib = A1 + 2B
I
+ E
I
+ 2E
2
, as before.
Factor groups are of particular importance in the spectroscopy of the solid state. A
detailed treatment of this topic lies outside the scope of the present work, but is
encompassed by the standard literature
I44
,5o,sl l,
8.8.2 Sitegroup analysis
An alternative, but sometimes less satisfactory, technique for studying vibrations in
solids is sitegroup analysis. It assumes that vibrational coupling between the
individual entities in the solid is negligible, so that the modes and activities may be
obtained in the customary manner, but using the site symmetry of the species in its
space group, Where the site symmetry is of higher degree than 2 (C
z
) but lower than
that of the crystal environment, sitegroup analysis splits the degeneracies of the
normal modes.
Potassium chromate crystallizes in space group Pnma (see Section 8,6.2) with four
fourmulaentities in the unit cell. The chromate ion [Cr04f has symmetry 43m
(Td), but occupies Wyckoff sites (c) of symmetry m (CJ in the unit cell:
4 (c) In ±{x, 114, z; Y2  X, %, Y2 + z}

From Section 7.4.1, we know that the symmetry 43m (for a free chromate ion)
leads to four normal modes, with activity in the infrared, for symmetry T
z
, and in
the Raman for A I + E + T
2
; the T
z
modes in the infrared and Raman are coincident.
These modes, together with three for translation and three for rotation make up the
fifteen degrees of freedom that we would expect for a single free chromate ion.
The spectra recorded for potassium chromate are more complex: single bands are
replaced by multiplets, and weak infrared activity is observed for the A1 and Etype
modes. It is a weakness of the sitegroup method, particularly with ionic crystals,
that coupling between the ions cannot be wholly ignored.
Factorgroup method for potassium chromate
In using the factorgroup method coupling is permitted, and we work on the whole
unit cell, preferably a primitive unit cell, as we did in the case of iron(II) sulfide (see
Section 8.8).
The factor group for space group Pnma is isomorphous with point group mmm
(D
Zh
) ' In the unit cell, there are eight K+ ions in two sets of (c), special equivalent,
positions, and four [Cr04f ions on one set of (c) positions, all of site symmetry m.
Problems 285
For the chromate ions, there are, thus, sixteen vibrational, twelve translational and
twelve rotational modes. They are representative of the crystal as a whole; those
belonging to E are doublydegenerate and those belonging to T
2
are triply
degenerate.
We set up a correlation table for the free ion of symmetry 4 3m to the site
symmetry m, and thence to the factor group mmm; we shall consider only the
vibrational modes. There are the frequencies 4Vl (AI), 4V2 (E), 4V3 (T
2
) and 4V4 (T
2
) ,
these sixteen frequencies making up the thirtysix internal modes. We note en
passant that the twelve translational and twelve rotational modes make up the total
of sixty degrees offreedom for the [Cr04f ions. To these, we could add the twenty
four translational modes for the eight K+ ions; there are no rotational modes for a
monatomic species.
In Figure 8.28, we present a correlation diagram for the vibrational modes
(chromate ions). Because of centrosymmetry, the crystal, unlike the free ion, does
not permit coincidence of the infrared and Raman frequencies. Comparison with the
actual data shows that the Raman frequencies predicted are observed, but fewer
infrared bands appear than expectedl596l J.
Free ion
Site symmetry Factor group
43m (J
d
) m (e. )
mmm ('D
2h
' j
4v A
,
1
2v
3
, 2v
1
,
'" A
v
1
, v
2
,
<, /'
4
<,
/' 9
/
V v
3
, V
,
/'
I
B
2' 4
)'A'( I
19
/ 'l \ 1
v
1
, v
2
, 2v
3
, 2v
/ I \ 1
B 4
/ I \ \ /
29
/ 'l y /
V
2'
v
3
, V
( I \ \/
B 4
4v
39
2
E ,,;1 " /' /' v2'
v
3
, V
A 4
'';; ! /\ ,)\
u
I" 1/ A \ v v
2
, 2v
3
, 2v
; <, /' \
B
1 ' 4
;/ > ~ I f : . __ \
1 u
'"  V 2'
v
3
, V
# / ~
B 4
~ // \
2u
V v
2
, 2v
3
, 2v
___I
v
/
B 1 ' 4
4v 4v
3u
3'
4 2T
2
Fig 8.28 Correlation diagram for the [Cr04r ion in potassium chromate; the site symmetry in
space group Pnma is m (C
s
) .
PROBLEMS 8
8.1 Rubidium bromide has the sodium chloride structure, with a density of 3350 kg
m". What are the dimensions of the repeat unit, and how many of them would be
contained in a regular crystal fragment of dimensions 0.10, 0.15, 0.20 mm (Rb =
85.47, Br =79.90; u = 1.6605 X 10
27
kg)'?
286
GrOUI) theory and crystal symmetry [Ch.8
 
8.2 In the tetragonal system the symmetry axes are 4 and/or 4 along Z, 2 and/or 2
along x andy, 2 and/or 2 at 45° to x and y in the xy plane (the directions [1I0] and
[110]). Are all combinations of these symmetry symbols permissible or necessary?
8.3 Explain the full meaning of the pointgroup symbols (a) mm2, (b) 622, and (c)
43m.
8.4 Two nets are described by the unit cells (i) a = b, y = 90°, and (ii) a = b, y =
120°. In each case (a) what is the symmetry at each lattice point, and (b) what are
the results of centring each unit cell? Give transformation equations as appropriate.
8.5 A lattice unit cell has the dimensions a = 0.5, b = 0.6, e = 0.7 nm, a = y = 90°,
~ = 120°. What system does it represent, and what is the symmetry at each lattice
point? Calculate the length of [31 2 ].
8.6 Show by means of sketches, or otherwise, that, in the monoclinic system, (a) B
== P; (b) A == C; (c) 1== C; (d) F == C; (e) C i= A. Give transformation equations for
(a)(d).
8.7 The relationships a '" b '" e, a.. = 90°,13", y '" 90°, 120° may be said to define a
diclinic system. Is it a new crystal system? If so, how so, and if not, why not?
8.8 A lattice is referred to a primitive unit cell of dimensions a = b = e = 0.700 nrn,
a.. = ~ = y = 109.47°. Calculate its volume. The transformation
a' = b + c
h' = a + c
c'=a+b
leads to a centred lattice unit cell. Determine the system, lattice type, unit cell
dimensions, volume, and point symmetry for the centred unit cell.
8.9 Sketch the WignerSeitz cell for a cubic F lattice.
8.10 For the space groups (a) C2/e (origin at I on the e glide), (b) Peal, (origin on
  
2)), (c) Pbea (origin at I), and (d) P4 2
1
e origin on 4), (i) list the crystal system
and point group, and (ii) write the full meaning of the symbol, including the
orientation of the symmetry elements with respect to the crystallographic axes.
8.11 Set up Seitzoperator symbols for 4 along the Z axis and a eglide plane at y =
0, both acting on a point rex, y, z). Determine the corresponding matrix equations,
and find the nature and orientation of the symmetry operation arising from the
combination c 4. Give the space group symbol for the combination, assuming a P
unit cell.
8.12 The Seitz symbol for a general space group rotation is {Rlt}, where t need not
be zero. Evaluate the effect of {Rlt}"r, where n is an integer? Hence, determine the
number of possible crystallographic screw axes.
8.13 Determine the general equivalent positions for space group Pbam, with the
origin on bam. Draw a space group diagram. Confirm that mab = 1 for this space
group. Transform the origin to I (21m) and obtain the revised coordinates. What is
the full symbol for this space group?
Problems 287
8.14 What are the Seitz symbols for the symmetry operators in space group P4nc,
with the origin on the fourfold axis? Justify the fact that a point x, y, z reflects across
an m plane at (q, q, z) in the tetragonal system to the point q  y, q  x, z. List the
general equivalent positions and draw a diagram to show the general equivalent
positions and symmetry elements for this space group.
8.15 Indicate the isomorphous nature of D
2h
and Pbam. What character table would
be suitable for a factorgroup analysis in space group Pbam?
8.16 By means of drawings, or otherwise, show that, in the monoclinic system, Pa ==
Pc == Pn, but that Ca == Cm and Cc == Cn.
8.17 List the general and special equivalent positions for space group P2
1/c,
in their
correct sets and with their point symmetries.
8.18 A 4
1
screw axis lies along the line [0, 0, z]. Formulate the corresponding Seitz
operator, and list the coordinates of the point derived from x, y, z through the action
of this operator. Formulate and name the inverse operator, and list the coordinates
obtained from x, y, z through this operator.
8.19 Why are the pointgroup symbols (often used) 41mmm and 61mmm
unsatisfactory for ~ mm and ~ mm, respectively?
m m
8.20 A carbonyl compound M(COh(CifI6) crystallizes in space group P2
11m,
with
two molecules in the unit cell; M is a species such as chromiun. (a) What can be
deduced about the molecular symmetry and its site symmetry in the crystal? (b)
What is the factor group for this crystal? (c) What is the symmetry of the MC0
3
moiety? (d) Use the six Co vibrators to generate a representation for the factor
group, and reduce it. (e) How many infrared and Ramanactive vibrations are
predicted? (f) Will they be coincident? If so, how so, and if not, why not?
Appendix 1
Stereoviews and models
Al.I STEREOVIEWS
The representation of molecular and crystal structures by stereoscopic pairs of
drawings has become commonplace. Computer programs exist that prepare
stereoviews from structural data. Two diagrams of a given object are necessary, and
they must correspond to the views seen by the eyes in normal vision. Correct
viewing of a stereoscopic diagram requires that each eye sees only the appropriate
half of the complete illustration, and there are several ways in which it may be
accomplished.
I. A stereoviewer may be purchased for a modest sum. The pair of stereoscopic
drawings may be viewed directly, and the threedimensional image appears centrally
between the two given drawings. Two suppliers of stereoviewers are:
(a) Casella & Co Ltd, Regent House, Britannia Walk, London Nl 7ND;
(b) TaylorMerchant Corpn, 212 West 35th Street, New York. NY 10001.
2. The unaided eyes can be trained to defocus, so that each eye sees only the
appropriate diagram. The eyes must be relaxed and look straight ahead. This
process may be aided by placing a white card edgeways between the two drawings.
It may be helpful to close the eyes for a moment, then open them wide and allow
them to relax without consciously focussing on the diagram.
3. A simple stereoviewer can be constructed with ease. A pair of planoconvex or
biconvex lenses each of focal length approximately 100 mm and diameter
approximately 30 mm is mounted between two opaque cards such that the centres of
the lenses are approximately 63 mm apart. The frame must be so shaped that the
lenses may be brought close to the eyes. Figure ALI illustrates the construction of
the stereoviewer.
Model with 84 Symmetry 289
Cut 3
I
•
8
Q
..      6.4cm    ~
I
1
E
o
'<t
I
I
I
"0,
0,
LL,
I
,
,
,
A
   11cm   
Fig A1.1 Simple stereoviewer. Cut out two pieces of card as shown, and discard the shaded
portions. Make cuts along the double lines. Glue the two cards together with the lenses Ez.
and E
R
in position, fold the portionsA and B backward, and fix the projectionP into the cut
at Q. View from the side marked B. (This type of stereoviewer is marketed by the Taylor
Merchant Corporation, New York.)
A1.2 MODEL WITH 8
4
SYMMETRY
The crystal model in Figure Al.2 may be constructed easily. This particular model
has been chosen because it exhibits an 8
4
symmetry axis, which is one of the
symmetry elements that is a little difficult to appreciate from plane drawings. A
good quality thin card should be used for the model. It is marked out in accordance
with the diagram, and then cut along the solid lines, discarding the shaded portions.
Folds are made, in the same sense, along the dotted lines, the flaps ADNP and
CFLM are glued and fixed internally, and the flap EFHJ is glued and fixed
externally. What is the point group of the model?
290 Appendix 1
Fig Al.2 Construction of a tetragonal crystal model:
NQ = AD = BD = BC = DE = CE = CF = KM = 100 mm;
AB = CD = EF = GJ = 50 mm;
AP = PQ = FL = KL = 20 rnm;
AQ = DN = CM = FK = FG = FH = EJ = 10 mm.
Appendix 2
Direction cosines and transformation of axes
A2.1 DIRECTION COSINES
In Figure A2.1, x, y and z are orthogonal axes, origin O. The three planes SOTL,
TORM and ROSN are coordinate planes, normal to the x, y and z axes, respectively.
The vector r is drawn from the origin to the point Ptx«; Yo, zo). Planes are drawn
through P, parallel to the coordinate planes. Then we have
where
OR = SN = LP = TM = Xo ,
OS = RN = MP = TL = Yo ,
OT = SL = NP = RM = Zo .
90°. ORP = OSP = OTP =
(A2.1)
(A2.2)
(A2.3)
(A2.4)
The angles A., Il, and v are the angles between the line OP and the x, y and z axes,
respectively. The direction cosines /, 171 and 11 of the line OP are defined as the
cosines of these angles; thus,
1
=
COS (A)
}
m =
eos(ll)
(A2.5)
n
=
eos(v)
zext s :
L
M
Byaxis
.,.;lL__+.......,. .
R
xaxiS/w_1W';
Fig. Al.l The vector r from 0 to P makes angles A., ~ and v with the orthogonal axes x, y
and z, respectively. Planes NRM, LSN and MTL are parallel to the coordinates planes yOz. zOx
and .xOy, respectively.
292 Appendix 2: Direction cosines
From the diagram, we have
1 =
xo/lrl
}
m =
y /Irl (A2.6)
0
n =
zo/Irl
Since Irl
2
= x.o
2
+ yo2 + ZQ2, it follows that the sum of the squares of the direction
cosines ofa line referred to orthogonal axes is unity; thus,
P+ m
2
+ n
2
= 1. (A2.7)
Evidently, I, m and n are not independent; from any two given, the third may be
found from (A2.7). Thus, a direction in threedimensional space is fixed from a
knowledge of any two of the angles J" II and v.
A2.2 TRANSFORMAnON OF AXES
A transformation of axes refers to a change from one set of orthogonal axes to
another, without a change of origin. Consider the vector r from the origin 0 to the
point P, Figure A2.2, having components r" r: and rs with respect to the x, y and z
axes; r', ' r ~ and r ~ are the components with respect to the transformed axes x', y'
and z' and, for clarity, only x' and r'l are shown. The component r', is the
resolution of r on to the x' axis, and may be obtained by resolving rl, rz. rs, as
though they were vectors, along x'. Thus, if the directions cosines of r', (and x')
with respect to the x, y and z axes are III, lvz and 1
13
, then
the sum of the projections of rj, r2 and rs on to r', . Similarly,
r 2 = 1
21
rj + 1
22
rz + 123r3 ,
r, = 1
31
rl +1
32
rz +1
33
rs .
From the result of (A2. 7), we have
3
L1~ k = 1 Ci = 1, 2, 3).
k=l
Treating r 'I and r ~ as vectors and forming their dot product leads to
(A2.8)
(A2.9)
(A2.lO)
(A2.11)
A2.2] Transformation of axes
Zaxis
yaxis
293
Fig A2.2 Orthogonal axes x, y and z are transformed to the set x', y/ and z', of which only x'
is shown. Vector r, from 0 to P, resolves into n. r2 and r'J along the directions x, y and z,
respectively; r '} is the resolution of r, on to the x' axis, and similar components may be set
up with respect to y' and z',
r ' • r ' = a == 1 1 r
2
+ 1 1 r
2
+ 1 1 r
2
.
1 2 11 21 1 12 22 2 13 23 3
(A2.12)
Since rj, Y2 and Y3 are not, in general, zero it follows that cross terms, such as lik ~ k (j
'* k) are zero, and the result may be summarized as
3
L1ik
1
jk
k=l
where 8ij is Kronecker's delta.
==
o. o.
1)
CA2.13)
Appendix 3
Stereographic projection and spherical trigonometry
A3.1 STEREOGRAMS
The stereographic projection, or stereogram, is a convenient way of representing a
set of symmetry directions in threedimensional space by means of a two
dimensional drawing, because it preserves the values of the angles between these
directions. We develop the projection with respect to the idealized crystal in Figure
A3.1.
From the centre 0 of the crystal, lines are drawn perpendicular to all faces of the
crystal. A sphere of arbitrary radius and centre 0 is described about the bundle of
radiating normals, produced as necessary to intersect the sphere, so as to form a
spherical projection of the crystal, Figure A3.2.
d
c
J....
9
e
b
a
Fig. A3.1 Ideal cubic crystal showing faces parallel to a cube, b, e and d, to an octahedron, r,
q, n and m, and to a rhombic dodecahedron.j', G, g, c, p and o. Each face shown has a related,
parallel face on the crystal; for example, b (shown) is related to b' on the opposite side of the
model. (Is it centrosynunetric?)
A3.I]
e'
Stereographic projection
p'
p
e
295
Fig AJ.2 Spherical projection of the crystal in Fig. A3.1, showing the intersections of the
normals with the sphere.
In Figure A3.3, the plane of projection is marked ABeD, and it intersects the
sphere in the primitive circle. The portion of the plane of projection enclosed by the
primitive circle is the primitive plane, or just the primitive. Next, the point of
intersection of each normal with the upper hemisphere is joined to the lowermost
point P on the sphere. The intersection of each such line with the primitive
represents the stereographic projection, or pole, of the corresponding face of the
crystal, and is marked by a dot; for example, the intersection R becomes the pole r.
If the crystal is orientated with respect to the sphere such that the vertical
direction del in the crystal is the diameter P'P of the sphere, then the normals to the
facesg, b.f, e, g', h',j and e' intersect the sphere in the primitive circle. We choose
further to orientate the stereogram so that the normal to face b on the crystal is
along the x axis. Clearly, lines drawn from P to points of intersection on the lower
hemisphere will meet the plane of projection outside the primitive circle. In order to
avoid increasing the size of the stereogram, such intersections are joined to the
uppermost point P' on the sphere, and the corresponding poles marked by open
circles.
296 Appendix 3: Stereographic projection
p'
p
Fig A3.3 Development of the stereogram from the spherical projection; r is the pole of R,
andS = OPtan(<t>/2).
The completed stereogram is shown in Figure A3.4. An important feature of the
stereogram is that distances on the stereogram are true measures of the angles
between crystal faces, so that the angular relationships of the normals (and the
crystal) are preserved in the projection.
All circles drawn on the sphere project as circles[8] on the stereogram. Thus, all
lines like ZiZ; are arcs of circles: they are projections of great circles on the sphere
(Figure A3.2). A great circle is the trace on the sphere made by a plane that passes
through the centre of the sphere; it is like a line of longitude on the globe. When
several faces on a crystal have a common direction in the crystal, they are said to lie
in one and the same zone, and the common direction is the zone axis. The zone axis
for the poles that are labelled 0, q, b, m, 0', q', b', m' in Figure A3.2 is normal to the
face p (Figure A3.1) and, in this particular example, it is also a twofold rotation
axis. The pole of a zone circle is the stereographic projection of a point on the
sphere that is 90° away from all points on the zone circle; in this example it is the
pole p (or p').
A3.2] Spherical triangles
b'
x axis
297
(A3.I)
(A3.2)
Fig. AJ.4 Completed stereogram of the crystal in Fig. A3.1.
As well as representing the faces on a crystal, the stereogram may be used to show
bond directions from a central atom, and other similar aspects of pointgroup
symmetry.
AJ.2 SPHERICAL TRIANGLES
Figure A3.5 shows a spherical triangle ABC formed on the surface of a sphere,
centre 0, by the intersections of great circles of which AB, AC and BC form parts.
The arcs a, band c are the sides of the spherical triangle, and its angles are
represented by the letters A, Band C. The sides are measured by the angles that they
subtend at 0; thus, side a is measured by the angle BOC. The angle A is measured
by the angle between the tangents at A to the arcs AC and AB: it is the dihedral
angle between the planes AOB and AOC, and is equal to the plane angle pAQ.
Similar definitions apply to the other elements of the spherical triangle
AJ.2.1 Formulae for spherical triangles
A spherical triangle is determined completely by its six parts, the sides a, b, c, and
the angles A, Band C. They are connected by the equations of spherical
trigonometry, of which we shall consider two.
In the trianglesAPQ and OPQ (Figure A3.5), we have
PQ2 = Ap
2
+ AQ2 _ 2 APAQ cos(A) ,
PQ2 = or + OQ2  2 OP OQ cos(a).
Subtracting (A3.1) from (A3.2) and rearranging, we obtain
OP
2
_Ap
2
+ OQ2 _AQ2 = 2 OP OQ cos(a)  2 APAQ cos(A) . (A3.3)
Since oAQ = oAp = 90°,
OA
2
= OQ2 _AQ2 (A3.4)
298
Thus,
or
Hence,
Appendix 3: Stereographic projection
OA
2
= OP OQ cos(a)  APAQ cos(A) ,
cos(a) = (OA/OQ)(OA/OP) + (AQ/OQ)(AP/OP) cos(A) .
cos(a) = cos(b) cos(c) + sin(b) sin(c) cos(A).
(A3.5)
(A3.6)
(A3.7)
Similar formulae can be obtained for cos(b) and cos(c) by cyclic permutation. By
forming cos
2(A)
= 1  sin
2(A)
from (A3.7), and similarly for cos
2(B)
and cos\C), it
may be shown that
sin(A)/sin(a) = sin(B)/sin(b) = sin(C)/sin(c) . (A3.8)
z axis
y axts
Fig. AJ.5 Spherical triangle ABC on a sphere, centre 0; APQ is the tangent plane to the
sphere atA.
A3.2.2 Polar spherical triangles
In Figure A3.6, ABC is a spherical triangle on a sphere, centre O. Let an arc B'C'
be, at all points on it, 90° away from the point A; thus, A is the pole of the great
circle of which B'C' is an arc. Similarly, Band C are the poles of the arcs A'C' and
A'B', respectively, so that triangle A'B'C' is the known as the polar triangle of
triangle ABC. By reciprocality, triangle A'B' C' is the polar triangle of triangle ABC.
Let the arcs AB and AC be produced to cut B'C' in D and E, respectively. Since A
is the pole of DE, DE is a measure of the angleA. But B'E + C'D = B'C' + DE and,
because B' and C' are the poles of CE and BD respectively, B'E = C'D = 90°. Thus,
B'C' + DE = a' + A = 180° and, since triangles ABC and A'B'C' are polar to each
other, we have the totality of relationships
A3.2] Spherical triangles 299
a = 180
0
 AI
}.
b = 180
0
 B
I
(A3.9)
C = 180
0
 C
I
a
l
= 180
0
 A
}
b
l
= 180
0
 B
(A3.10)
c
l
= 180
0
 C
A'
Fig. AJ.6 Spherical triangle ABC and its polar spherical triangle A'S'C'.
Substituting for a', b' c' and A' in (A3.7) and rearranging,
cos (a) =
cos(A) + cos(B) cos (C)
sin(B) sin(C)
(A3.11)
Similar equations may be formulated for b, c, a', b' and c' by the usual cyclic
permutation.
AJ.2.3 Example stereograms
We shall make use of stereograms in this book to represent symmetry directions
radiating from a central point bond directions from a central atom, or normals to
crystal faces from a central point in the crystal. In the two examples here, Figure
A3.7 shows the symmetry operation S4, present in the example of Figure 2.4; it
represents point group 54. Figure A3.8 shows the symmetry element C
4
, with two
fold axes C~ normal to the C
4
axis; it represents point group D
4.
We remark here that the twofold axes (C~ ), x (top to bottom) and y (left to right),
as depicted in Figure 3.8, are equivalent under the operation C
4;
they fall into the
same symmetry class. The other twofold axes ( C ~ ) are also equivalent under C
4
but
A3.2] Spherical triangles 301
(a)
(b)
Fig AJ.I0 Stereograms of Figure A3.9 in the revised notation: the relative heights of the
points in Figure A3.9 are now indicated by the + and  signs; in (b), the enantiomorphous
characterof points (2) and (4) with respect to (I), and (3) is shownby means of the commas.
emphasises first the threedimensional character of the object that is represented, by
means of +and  signs against the circles (poles); secondly, the chiral natures of the
parts related by an improper rotation (or reflection) are indicated by the comma
within symmetryrelated circle. Other symbols on the stereograms represent
symmetry axes.
In Figures A3. 9b and A3.1Ob, note the symbol for a C
2
axis lying inside the
square: C
2
is a subgroup of S4. Other symmetry symbols will be explained as they
arise. Further discussions on the stereographic projection, including a full resume of
symmetry notations, are well reported in the literature{1,8.
23
1.
Appendix 4
Matrix diagonalization by Jacobi's method
We consider a 3 x 3 matrix Q, given by
[;"
1 1
]
12 13
Q = 1 1
CA4.1)
21 22 23
1 1 1
31 32 33
Its transpose is obtained by interchanging the rows and columns:
[;"
1
1
31
]
21
Q = 1 1 . CA4.2)
12 22 32
1 1 1
13 23 33
Let us consider that the Ii] terms are the direction cosines defined and discussed
under the transformation of axes in Appendix 2. Then it follows from (A2.B) that
QQ=E, so that Q= Q\ and matrix Qis orthogonal (see Section 2.5.3). Thus, an
orthogonal matrix of order 3 can be used to represent the rotation of one set of
orthogonal coordinates to another set: for a clockwise rotation e of the x,y frame
about a fixed z axis, that is, in the xy plane, the matrix Q becomes
Q =
[
cos Ia)
sinCS)
o
sinCS)
casCS)
o
CA4.3)
In Figure A4.1, this result is used for the special case of an orthogonal matrix of
order 2, for the rotation just described. The new frame x',y' is obtained by the
transformation
=
(
ca s CS ) sinCS) ) (x)
sinCS) casCS) y
= Q ( ; I
CA4.4)
The same matrix applies to an anticlockwise rotation of the vector r, the axes
remaining stationary.
The Jacobi diagonalization may be considered as an iterative procedure for
selecting the diagonalizing matrix Q based on the transformation of a position
vector r, by an anticlockwise rotation e, to a new position r', and is applicable to
symmetric matrices. The matrix Q here is the appropriate twodimensional part of
the matrix in (A4.3), and the transformation is given by (A4.4). The matrix Q is
orthogonal, as we have demonstrated, and orthogonal transformations do not change
the angle between the coordinate axes.
Matrix diagonalization 303
yaxis
y'axis
1"'==:::......,:' xaxis
x'axis
Fig A4.1 A clockwise rotation of the XJ' frame through an angle e. If any vector r makesan
angle ~ withthe x axis, thenx =r cos ~ andy =r sin ~ , where r = [rl; simple manipulation
nowleadsto Qin (A4.4) [seealso(2.57)].
If we now apply this diagonalizing matrix Q to the matrix A used in Example 2.7
(see Section 2.5.4), we write
[
COS 8 sin e) [1 2) [COS 8 sin 8) [i\ 0)
8
= 0
1
i\z . CA4.5)
sin 8 cos 8 2 1 sin 8 cos
Expanding the lefthand side of (A4.5), we obtain
[
[ COS
Z
(8 ) +4 COs(8)sinC8)+sinzC8)]
[2coSz(8)2sinzC8)] [cosz(8)4
[2cos
z
(8)2sin
z
(8)]]
cosCS)sin(8)+sin
2C8)]
[
0
\ i\oz] = °
(A4. 6).
This equation is satisfied for offdiagonal terms equal to zero, that is, for
2 cos
2(8)
 2 sin\8) = 0
or
tan(8) = 1,
(A4.7)
(A4.8)
304 Appendix 4: Matrix diagonalization
so that the desired value of 8 in this example is 45°. Substituting this value of 8 into
the diagonal terms (A4.6) gives the diagonalized matrix
(A4.9)
identical to the result that we obtained in Example 2.7. For any matrix A, given by
A =
[
a11a12]
a a '
21 22
(A4.10)
the value of8 in the diagonalizing matrix Q in (A4.4) is given, in general, by
tan(28) = 2aI2/(all  a22) . (A4.11)
Then, any 2 x 2 symmetric matrix A may be diagonalized through the similarity
transformation
(A4.12)
Examples of the Jacobi diagonalization are given in Section 2.5.4 and by Problem
2.9.
Appendix 5
Spherical polar coordinates
AS.I COORDINATES
The polar coordinates r, eand are defined by
x = r s int e ) cos(¢)
}
y = r sinCe) sin(¢)
(AS.l)
z = r cos (e)
where
r
2
= X
2+y2+i.
(A5.2)
AS.2 VOLUME ELEMENT
We need to express the volume element d. in spherical polar coordinates. Consider
the volume element d. shown in Figure A5.1; it corresponds to the quantity dx dy dz
in Cartesian coordinates. It is a straightforward matter to determine the magnitudes
of the sides of the volume element, which may be taken to be parallelepipedal.
Hence,
d. =? dr sinCe) de (A5.3)
The limits of the polar variables that correspond to x, y and z each between 00 to +CX)
are
0 ::s r ::s +00
}.
0 ::s e ::s 7l
0
::s ¢ s
271
(AS.4)
These limits would enclose a sphere of infinite maximum radius.
A5.3 LAPLACIAN OPERATOR
The Laplacian operator is defined by
= (AS.S)
In polar coordinates it takes the form[20
j
2
sin (e)
1
+ sin (e)
a
2
a¢2
(AS.6)
306 Appendix 5: Spherical polar coordinates
zaxis
yaxis
Fig. AS.l The volume element dt in spherical polar coordinates.
Appendix 6
Unitary representations and orthonormal bases
A6.1 DERIVING AN UNITY REPRESENTATION IN C
3v
The solution of the wave equation leads to 2p orbitals that may be written in the
form
P+
1
= fer) sineS) exp(i</»
P1
= fer) since ) exp(i</»
Po
= fer) cas(S)
}
(A6.l)
Here Po is equivalent to pz, and the two linear combinationsl'Y'" P+I ± P_I lead to p,
and py. An anticlockwise rotation of a vector r by 120° may be represented by
exp(i2n/3), which we shall denote by s; the conjugate f:* is exp(i2n/3). The
transformation operator Oc has the property ofrotating a vector at the location r, 8,
~ to a new location r', 8', ~ ' , where r' =r, 8' =8 and o' =~ + a. Thus, from (5.24),
Ocf{r', 8', ~ ' ) =f{r, 8 , ~ ) =f{r', 8 ' , ~ '  a), (A6.2)
or generally, since the extreme lefthand and righthand terms are both primed, we
have
Ocf{r,8, ~ ) = f{r, 8, ~  a) .
Applying this operator to the p orbitals, with a = 21[/3, we obtain
(A6.3)
=
=
fer) sineS) exp[i(</>  2n/3)]
fer) sineS) exp(iS) exp(i2n/3)
} (AUl
In full, for the three p orbitals (a row vector), we write
=
•
£ X P + 0 x p + 0 x P
+1 1 0
o x p + £ X P + 0 x Po
+1 1
I
(A6.5)
Thus, the matrix corresponding to Oc is
[
:
£ .
D(C) =
3
o
o
(6.6)
308 Appendix 6: Unitary representations
We take another operation, (J (see Figure 4.2); it moves a vector from r, 8, to r',
8', where r' = r, 8' = 8 and =  where is the angle of anticlockwise
rotation of the (J', plane from the plane of XZ, that is 60°. This operation is also the
reflection of the vector across the a ; plane. Let the transformation operator be 0,,;
then
O"P'1
= fer) sineS) exp[i(2n/3
= fer) sineS) exp(i2n/3)
(A6.7)
=
cp .
1
In full, for the three p orbitals, we have
O"p,j
= a x p + C x P + a x p
+1 1 0
O"P.I
=
•
e xp +Oxp +Oxpo
+1 1
(A6.8)
Q"Po
= a
so that the corresponding Dmatrix is
[
D(O .) = <
(Jv
•
e
a
a
].
(A6.9)
If we continue in this way for all operations in C
3v
, we obtain six matrices in all, as
follows:
D(El = [
[
O
CO
D(c
1
)
3
D(U;) = [
a
1
a
O.
e
a
•
e
a
a
[
D(C )
3
D(U.) = [ !
a
e
a
1
a
a
e
a
a
(A6. 10)
These matrices and those of (4.14) and (4.17) are all representations of point goup
C
3v
• Each of them leads to the same reducible representation, which reduces to AI +
E:
A6.1) Deriving unitary representation 309
fred
E
3 o
O'v
o
E
3 o 1
In general, two representations of a point group by matrices D"JR) and Dp(R) are
equivalent if a matrix Qexists that obeys (4.21) for all operations R.
We can find the matrix Qby noting first that the p orbitals formulated in (A6.1)
are related to the real forms px, pyand pz by the equations
=
P+
1
=
(1/v2)(p + ip
)
x y
P1
=
(1/v2)(p  ip )
x y
Po
=
Pz
The inversion of these equations is readily obtained:
(l/v2) (p + ip
+1 1
= (1/v2) (p + ip )
+1 1
Pz
}
(A6. 11)
(A6.12)
Thus, the matrix Q is, from (A6.12)
Q = [ : ~ ~ :
i/v2
i/v2
o
(A6.13)
We apply (4.21), where D
2
(C
3
) is taken from (4.3) with 8 = 120°:
[11>'2 1/"'2
0] r1/2
v3/2
0] [1/,.,2
1/v2
~ ]
D (C ) = 1/v2 i/v2 o v3/2 1/2
o i/v2 r.vz
1 3
o 0 1 0 0 1 0 0
= ri(,.,3 : 1l/2
0
~ ]
i (v3  1)/2
(A6.14)
0
The expression i(...J3 + 1)/2 is simply [cos(2n/3)  i sin(2n/3»), or exp(i2n/3), which
is E* in (A6.6); i(...J3  1)/2 is exp(i2n/3), or E. Thus, (A6.14) is equal to (A6.6),
which latter was produced more easily by the transformation operator method.
That the matrices in (A6.IO) are unitary follows readily from Section 2.5.5. For
example, the inverse of D( 0' " ) is
v
310 Appendix 6: Unitary representations
=
[
 E
o
o
CA6.15)
which is equal to
A6.2 UNITARY REPRESENTATIONS FROM ORTHONORMAL BASES
Let \V" \V2, .... , \Vn be a set of orthonormal functions in ndimensional space. By
definition Csee Section 5.3), the scalar product \Vi' \jIj is given by
= I t/J. dT
1 )
=
o...
1)
CA6.16)
From Section 5.3.1, we know that symmetry operations R can be paralleled by
transformation operators OR that are unitary; thus,
If we now apply (5.36) to this equation, we obtain
0 ... CA6.17)
1)
= (5 ..,
1)
n n
I {LDCR)ki t/J
k
LDCR) 1j t/J
1
} dT
k=l 1=1
which may be recast as
n n
L LDCR)ki DCR) 1j I t/J
1
dT =
k=l 1=1
From (A6.16), we replace the scalar product f\Vk* \VI de by Okl:
O..'
1)
CA6.18)
n n
L LDCR)ki DCR) 1j °k1
k=l 1=1
= o. o.
1)
CA6.19)
A nonzero result for CA6.19) is obtained for k = I, whereupon the double summation
is reduced to single status:
n
LDCR)ki DCR)kj =
k=l
o...
1)
CA6.20)
If we transpose D*CR)ki, we obtain 5 * CR)ik, equivalent to the adjoint of DCR);k:
A6.2] Unitary representations from orthonormal bases 311
n
Ln(RJ
i k
D(RJ
k j
k=l
= 0 .._
1)
(A6.21)
Consideration of Section 2.5.3 shows that this equation represents the product of
two matrices, and a nonzero result requires that their product shall be the identity
matrix, E; thus,
and
5 *(R) D(R) = Dt(R) D(R) = E,
Dt(R) =D
1
(R),
(A6.22)
(A6.23)
so that the matrices that represent unitary transformation operators are, themselves,
unitary.
Appendix 7
Gamma function
The gamma function is useful in handling integrals that can be expressed in the
form
00
J x
n
exp(ax) dx,
o
(A7.1)
where a is a scalar constant. The gamma function fen) is defined by the integral
equation
f(n)
=
00
f
t
n 1
exp( t) dt.
o
(A7.2)
The following results are important:
(a) For n > 0 and integral,
fen) = (n  I)! ;
(b) For n > 0,
f(n + 1) = nf(n) ;
if n is also integral, it follows that
f(n + 1) = n! .
(c) f(ll2) = In .
EXAMPLE A6.1. Evaluate the integral
J
oo x3
exp(2X) dX.
o
Let x =tl2 so that dx =dtl2. Then,
(A7.3)
(A7.4)
(A7.5)
(A7.6)
00
= (1/16) f
o
3
t exp (  t ) d t .
Using (A6.2) and (A6.5)
1= (1/16) [(4)= 3!/l6 = 3/8
As an alternative to the gamma function, or when the integration is between fmite limits, the
reduction formula may be used:
J
n (x
n)
n Jn1
X exp(ax) dx = a exp(ax)  a x exp(ax) dx. (A7.7)
Appendix 8
Overlap integrals
In discussing the LCAD technique (Section 6.2), we encountered the overlap
integral f'Vi lJ!i dr. Here, we will carry out the evaluation of this quantity in a fairly
simple case. Consider the overlap between two hydrogen Is atomic orbitals, I and 2.
Taking each AD to be of the form 'V = (na )"1/2 exp(r/ao), the overlap integral S
becomes
s =
1 00 1l 21l
3 JJJexp[(r
rra 0 0 0 1
o
The overlap system has cylindrical symmetry, and it is convenient to transform the
integral to spheroidal coordinates v and <p given by
(A8.2)
where R is the internuclear distance in units of ao; ranges from I to 00, v ranges
from I to +I and <p ranges from 0 to 27t. The volume element dr becomes (R
3
 dv d<p. The formulation of dr has been discussed exhaustively, albeit with
slightly different notations, in the literature\2425
1
. We rewrite (A8.1) as
J
2 J1 JOO 2 2
S = (R
3
/ 8 1l ) d¢ exp LRu) (Jl  v ) dv du,
o 1 1
Integrating first over <p leads to
J
1 JOO 2 2
S = (R
3/4)
dv exp CRu) (Jl  v).
1 1
Expanding (A8.4) gives
(A8.3)
(A8.4)
00 1 00
S = (R
3/4)J
2Jl2 exp(RJl)dJl  J v
2dv
J exp(RJl)dJl. (A8.S)
1 1 1
which reduces to
S = (R
3/4)J
2Jl2 exp(RJl) dJl  §J exp(RJl) dJl.
1 1
The reduction formula [see (A7.7)] then gives the required result for S:
S = exp(R) (l +R +R
2/3).
(A8.6)
(A8.8)
Appendix 9
Calculating LCAO coefficients
We examine the calculation of LCAO coefficients through a practical example with
the matrix A that arises in the application of the Huckel molecular orbital theory to
buta1,3diene:
A =
y
1
a
a
1
Y
1
a
a
1
y
1
(A9.1)
(A9.2)
where y = (0.  £ ) / ~ . Expanding det(A) leads to the equation
l3/+1,
which factorizes to
(l +y  1)(v2  Y  1) = 0, (A9.3)
whence y = ±[(I ± .J5)/2]; more generally, the program POLY, (see Appendix 12)
maybe used.
We return to the secular equations of the form of (6.34). The customary Huckel
approximations set H;; = 0., HiJ= H;; = ~ for i adjacent toj, otherwise HiJ = 0; Sij = 0,
and (0.  £.; ) / ~ = y. Then we obtain a set of simultaneous equations that can be
solved for the ciJ values in the ith molecular orbital. For i = 1, we write:
C
11
Y
c
a
a
=
a
12
c
C
12
Y
c
a
=
a
11
13
a
c
c
13
Y
c
=
a
(A9.4)
12
4
a
a
c
c
14
Y =
a
13
Solving by successive elimination, taking the rooty = (I + '1/5)/2, we have
CI2 = CIl (1 + .J5)/2,
Cn = CIl  Cl2 [(I + .J5)/2] = Cil (I + .J5)/2,
CI4 = Cn /[(1 + .J5)/2] = CII.
Normalizing through (5.15) leads to N = .J(5 + .J5). Hence,
ClI = 0.37175,
C22 = 0.60150,
C\3 = 0.60150,
CI4 = 0.37175.
The reader may wish to examine the other roots in a similar manner.
Calculating LCAO coefficients 315
The method of successive elimination becomes somewhat tedious with a
determinant of order 4 or more, and a more systematic approach is through the
cofactors defined in Section 2.5.3. The coefficients may be obtained from the
determinant of (A9.l) accordingto
C • = N Alj
1)
= (A9.5)
(A9.6)
where the subscript 1 in Alj shows that we form the required cofactors from the
first rowof the determinant; Mlj is the minor of alj, and N is a normalization factor
given, following (5.15), by
{ }
 1 / 2
N = L.
J
Applyingthis procedure to (A9.1), we obtain the following results, again using the
root (1 + "5)/2:
M
2
j
Ali
AU
C
Ij Ij
1
3
1 1 0.37175 Y  Zy
1  y
2
( 1 + ,J5)/Z (3 + ,JS)/2 0.60150 Z
3 y
(l + ,JS)/2 (3 + ,JS)/2 0.60150
4 1 1 1 0.37175
The remaining roots maybe treated in like manner.
If the solution of (A9.l) is carried out by the Jacobi diagonalization program
EIGN, first setting y = 0, then the eigenvalues are the energy functions (ex, 
and the eigenvectors are the coefficents cji. The tabulation below lists the total
results fromthis procedure:
j 1 Z 3 4
i
Y
i
Coefficients, c ..
1)
1 1. 6180 0.37175 0.60150 0.60150 0.37175
2 0.6180 0.60150 0.37175 0.37175 0.60150
3 0.6180 0.60150 0.37175 0.37175 0.60150
4 1. 6180 0.37175 0.60150 0.60150 0.37175
Appendix 10
Hybrid orbitals in methane
We have shown (see Section 604ft) that four hybrid orbitals on carbon are required
in forming SALCs for methane, point group Td: each consists of an s orbital
spanning Al , and three p orbitals spanning Tz. We list the symmetry operators and
their action on any three of the atomic orbitals \Vi (i = 14) for T
d
, and apply the
projection operators PA and Pr. . The tetrahedron model from Example 6.1 is useful
I 2
here, with the comers representing \VC\V4. We note that P
A
applied to any of the \Vi
leads to the same SALC; only three of the \Vi are needed t6 form SALCs with P
T2
;a
fourth so generated would not be linearly independent of the other three. The table
of OR\Vi (i = 13) follows:
E C C
2
C
3a 3a 3b
1/1
1
1/1
1
1/1
4
1/1
3
1/1
4
1/1
2
1/1
4
1/1
2
1/1
1
c
2
C
3b 3c
C
3d
c c C
2z 2y 2x
1/1
4
1/1
3
1/1
2
1/1
3
1/1
4
1/1
1
1/1
2
1/1
1
1/1
4
1/1
2
1/1
2
1/1
4
1/1
4
1/1
4
1/1
3
1/1
1
1/1
3
1/1
1
1/1
4
1/1
2
1/11
= 6(1/1 +
1
= 2(31/1
1
(AlD. 1)
(AlD.2)
=
(A10.3)
= 2(1/1 
1
1/1 +31/1 1/1).
234
(AlD.4 )
We can normalize these SALCs in the usual manner. However, we need to establish
(AlO.I)(AI004) in terms of s, Px, Py and Pr. We write (AlO.I) immediately in its
normalized form as
(AlO.5)
Appendix 10
which clearly represents the s orbital, because it has A1 symmetry.
We write (AIO.2) as a normalized, linear combination ofp orbitals; thus,
1
 1/1  1/1 _.h) = (c
2
+ c
2
2)1/2 (
v lL 1 2 3 'P 4 X Y + C
z
CxPx
317
where 1/...J12 is the normalization factor. Using the tetrahedron model, it is easy to
show that the operation C
3a
, along the direction of \1'1 has the effects:
so that (cxPx + cypy + czpz) in (AlO.6) transforms to (cxPy + Cypy + czPx). By
comparing coefficients, it follows that C
x
= C
z,
cy = cx, c, = c
y;
then,
=
(AlD.7)
Resolving \l'i (i = 14) into its components shows that the positive square root is
required for (AlO.7), and the normalization factor is now the constant 1/...J3.
If next we consider the operation C
3b
on \1'2, then
so that, using (AlO.3), (cxPx +Cypy + czpz) now transforms to (czPx  CxPy + cypz), and
in (AlO.8) the positive square root applies again:
1 (.h + 31/1  1/1
3
 1/14) =  P
y
+ p
z)'
(A10.8)
'P
1
2
By applying similar reasoning with C
3c
, \113 and (AI0.4), we obtain
=
(A10.9)
where we require the positive square root. Equations (AlO.7)(AlO.9) are readily
solved for px, py and p; Including (AlO.5), we now have the set, which can be
written in matrix form as
1 1 1 1
1/1
1
S
2 2 2 2
1 1 1 1
1/1
2
P
x
2 2 2 2
(A1O.1O)
=
1 1 1 1
1/1
3
P
y
2 2 2 2
1 1 1 1
1/1
4
P
z
2 2 2 2
318 Appendix 10
The 4 x 4 matrix term M of (AlO.lO) is orthogonal, as is easily confirmed; hence,
M:' = M, so that the hybrid orbitals become
1 1 1 1
1/11
    5
2 2 2 2
1 1 1 1
1/1
2
  

P
x 2 2 2 2
(A1O.ll) =
1 1 1 1
1/1
3
 
 
P
y 2 2 2 2
1 1 1 1
1/1
4
   
P
z 2 2 2 2
and their final forms may be written as
1/11
1
) = (5
+ P + P + P
2 X
Y
Z
1/1
2
1
) (5  P
x
 P + P
2
Y
z
(A1O.12)
1/1
3
1
)
= (5 + P
P
y
P
z 2 X
1/1
4
1
)
= (5  P
x
+ P 
P
z 2
Y
Reference to the character table for Td shows that T
2
is spanned by three product
forms that correspond to the orbitals d
xy
, d
yz
and dzx, as well as by Px, py and p; It
follows, therefore, that symmetry arguments alone applied to methane would predict
hybrids of the form either Sp3 and sd'. Chemical knowledge, such as the relatively
higher energy state of the d orbitals, may be invoked to show that Sp3 hybrids are
favoured energetically.
Appendix 11
Character tables and correlation tables for point groups
All.l CHARACTER TABLES
The character tables are presented in the order in which they appear in Table 3.5 of
the main text. The principal axis C; of highest degree n lies, normally, along the z
axis. Exceptions occur in point groups T, T
h
and T
d
, and only Td is of common
occurrence among chemical species; in these groups, the C3 axes lie along the
<Ill> form of directions in a cube or cubic lattice.
We have shown that certain point groups, and their character tables, may be
derived from the direct product of two others. This relationship may be indicated by
the partitioning of such tables by dotted lines; examples are C3h = C3 ® C. or D2h =
D
2
® C; Note that when the direct product involves C
i
, the subscripts 's' and 'u'
from C, are transmitted to the irreducible representations of the resulting group.
Groups C
n
(n = 16)
~
~
Cz
E C h = 2
2
A 1 1 z· R
2 2 2
Z ; x ; y ; xy ,
z
B 1 1 x' y; R' R yz; zx ,
x' y
E C C
2 i21l/3
3
C
3
C = e h =
3 3
A 1 1 1 R
2 2 2
z' Z ; x +y ,
z
t
•
E
e e
(x , y) ;
(R
x
'
R )
2 2
(x y , xy) ; (yz, zx)
•
y
e C
C
4
E C C C
3
h = 4
4 2 4
A 1 1 1 1 z' R
2 2 2
Z ; X +y ,
z
B 1 1 1 1
2 2
x y ; xy
E
t
i 1 i
}
(x, y) ; (R R ) (yz, zx)
i 1 i
x'
Y
320 Appendix 11
i21r/5 234
C E C C C C e = e h = 5
5 5 5 5 5
A 1 1 1 1 z : R
2 2 2
1
, z
z ; x +y
{
1
2 2
: }
E
e e e
(X, y l : (R , R ) (yz, ZX)
1

2 2 X
Y
1 e e e
{
2

::)
1 e e e 2 2
E (x y , xy)
2 2

1 e e e
i21r/6 2 5
C
6
E C C C
2
C C e = e h = 6
6 3 3 6
A 1 1 1 1 1 1 R
2 2 2
z· Z ; x +y ,
z
B 1 1 1 1 1 1
{

:}
E
1 e e 1 e
(x , y) ; (R , R ) (yz, ZX)
1


x
Y
1 e e 1 e
{
 
E
1 e e 1 e
e_}
2 2
xy)
2

(x y ,
1 e e 1 e e
Groups C. and Cj
E a
h
=
2
C.
2 2 2
A' 1 1
x· y; R z ; x ; y ; xy
,
z
AI I
1 1 Z; R' R yz; zx
x' y
Cj
E
h
=
2
2 2 2
A 1 1 R R R z ; x ; y ; xy; yz; zx
9
Z' x'
Y
A 1 1 Z; x·
Y
,
u
A direct product involving Cj , such as Cj ® ~ , may be studied to note the transfer
of the subscripts 'g' and 'u' from Cj to the product group C
2
h.
Appendix 11 321
Groups SIt (n =4, 6)
S4
E 5 C
53
h = 4
4 2 4
A 1 1 1 1
R .
2 2 2
Z .
x +Y
z'
,
1
2 2
B 1 1 1 z x y ; xy
E
{
1 i 1 i
}
(x, y) ; (R , R ) (yz, zx)
1 i 1 i
x
Y
2 5
S
E C C i 5 5
12Tl/3
h = 6 c= e
6 3 3 6 6
A 1 1 1 1 1 1 R
2 2 2
Z .
X +y
q
Z
,
{
•
c. c)
2 2
E
1 e e 1
(R , R )
(x y , xy ) j
q
•
x
Y
1 e e 1 cc (yz, zx)
A 1 1 1 1 1 1 z
u
{
•
c·c.}
E
1 e e 1
(x, y)
u
•
1 e e 1 c c
Groups G"v(n =26)
G
E C cr
v
cr' h = 4
v
2v 2
2 2 2
A 1 1 1 1 z z j x;
Y
1
A 1 1 1 1 R xy
2
Z
B 1 1 1 1 x; R zx
1 Y
B
2
1 1 1 1 y; R yz
x
cry is the plane xz and o ~ the plane yz. If they are interchanged, B
1
and B
2
are
spanned by y, R
x
, yz and x, Ryr zx respectively; the character of B
1
under (Tv remains
as (+)1.
G
3v
E 2C 3cr
v
h = 6
3
A 1 1 1
2 2 2
Z Z ; x +y
1
A 1 1 1 R 2 2
, xy ) : (yz, zx) 2 z (x y
E 2 1 a (x , y) ; (R , R
)
x
Y
322 Appendix 11
C
4v
E 2C C
2o
v
2o
d
h = 8
4 2
A 1 1 1 1 1
2 2 2
Z Z ; x +y
1
A 1 1 1 1 1 R
2 Z
B 1 1 1 1 1
2 2
1
X y
B 1 1 1 1 1 xy
2
E 2 0 2 0 0 (x, y) ; (R , R
) (yz, zx)
x y
2a
v
contain z, x, and z, y; 2ad contain z and lie at 45° to x and y.
C
sv
E 2C 2C
2
50
v
<:
= 72° h = 10
5 5
A 1 1 1 1
2 2 2
Z Z ; x +y
1
A 1 1 1 1 R
2 z
E 2 2cos < 2cos
2<
0 (x , y) ; (R , R
)
(yz, zx)
1 x y
2 2
E 2 2cos 2< 2cos
c
0 (x y xy)
2
,
C
E 2C 2C C
3o
v
3o
d
l
h = 12
6v 6 3 2
A 1 1 1 1 1 1
2 2 2
Z Z ; x +y
1
A 1 1 1 1 1 1 R
2 z
B 1 1 1 1 1 1
1
B 1 1 1 1 1 1
2
E 2 1 1 2 0 0 (x , y) ; (R , R
) (yz, zx)
1 x y
2 2
E 2 1 1 2 0 0 (x y xy)
2
,
The use of O"d here (and in C
4v
) is not strictly according to the rules, but is
conventional (see Note 2 to Table 3.5).
C
2h
E C i oh
h
=
4
2
1 1 R
2 2 2
A 1 1 z ; x ; y; xy
9
Z
B 1 1 1 1 R· R yz; zx
9
x'
Y
A 1 1 1 1 z
u
B 1 1 1 1 x;
Y
u
Appendix 11 323
C
3 h
E C C
2
crh
5
55
121l/3
h = 6 £ = e
3 3 3 3
A' 1 1 1 1 1 1 R
2 2 2
Z  X +y
Z'
,
{

:}
£'
1 e e 1 e
(x, y)
2 2


(X y , xy)
1 e e 1 e
A' ,
1 1 1 1 1 1 z
{
 £}
E' ,
1 e e 1 £
(R , R ) (yz,


X y
zx)
1 e e 1 £ £
3
C E C C C i
53
crh 5
h = 8
4h 4 2 4 4 4
A 1 1 1 1 1 1 1 1 R
2 2 2
Z ; X +y
g z
B 1 1 1 1 1 1 1 1
2 2
g
X y ; xy
t:
{
1 i 1 i 1 i 1 i
}
(R
x
'
R ) (yz, zx)
g
1 i 1 i 1 i 1 i
Y
A 1 1 1 1 1 1 1 1 z
u
B 1 1 1 1 1 1 1 1
u
t:
{
1 i 1 i 1 i 1 i
}
(x, y)
u
1 i 1 i 1 i 1 i
i21l/5
7 3 9
4 2
C E C C C
3
C crh 5 5 5 5 £ = e h = 10
5h 5 5 5 5 5 5 5 5
A' 1 1 1 1 1 1 1 1 1 1 R
2 2 2
Z ; X +y
Z
{
2 2

2 2 }
£'
1 e e e e 1 e £ £ £
(x, y) (yz, ZX)
1

2 2

2 2
1 e e e e 1 e £ £ £
{
2

2 2

::}
2 2
£'
1 e e e e 1 e c e
(x y ,
2 2

2 2

xy)
1 e e e e 1 e e c
A' ,
1 1 1 1 1 1 1 1 1 1 z
{
2 2

_£2 _£2_£ }
E' ,
1 e e c e 1 £
(R R
) (yz, ZX)
1

2 2  2 2
X'
Y
1 e e e e 1 £ £ £ £
{
2

2
2  2
E' r
1 e e e e 1 £ £ £ c }
2 2

2
2  2
1 e e e e 1 £ £ £ £
324 Appendix 11
2 5 5 5
C E C C C C C
i
S S (lh S S i21l/6 h = 12
6h 6 3 2 3 6 3 6 6 3 C = e
A 1 1 1 1 1 1 1 1 1 1 1 1
2 2 2
Z ; x +y
g
B 1 1 1 1 1 1 1 1 1 1 1 1
g
• • • •
E
{
1 c c 1 c e 1 c c 1
c. c }
(R , R ) (yz, zx)
19
• • •
x
Y
1 c c 1 c e 1 Cc 1 c c
{
• • • •
1 c c 1 c c 1 c c 1
c C.}
2 2
xy) E
• • •
(X y ,
2g
1 c c 1 c c 1 c c 1 c c
A 1 1 1 1 1 1 1 1 1 1 1 1 z
u
B 1 1 1 1 1 1 1 1 1 1 1 1
u
{
• • •
C.C·}
E
1 c c 1 c e 1 c e 1
(x , y)
lu
• • •
1 c c 1 c c 1 c e 1 c c
{
• • • •
:.}
E
1 c c 1 c c 1 e c 1 e
2u
• • •
1 c c 1 c c 1 e c 1 e
Groups 0" (n =26)
O
2
E C (z) C (y) C (x)
h = 4
2 2 2
A 1 1 1 1
2 2 2
Z ; x· y ,
B 1 1  1  1 z· R xy
1
,
z
B 1 1 1  1 y; R zx
2
Y
B 1 1  1 1 x· R yz
3
,
X
0
3
E 2C 3C'
h = 6
3 2
A 1 1 1
2 2 2
1
Z ; x +y
A 1 1 1 z; R
2 Z
E 2 1 0 (x, y) ; (R , R )
2 2
, xy }; (yz, zx)
x y
(x y
Appendix11 325
D4.
E 2C C 2C
'
2C' I
h = 8
4 2 2 2
A 1 1 1 1 1
2 2 2
Z ; x +y
1
A 1 1 1 1 1 z; R
2 Z
B 1 1 1 1 1
2 2
1
X y
B 1 1 1 1 1 xy
2
E 2 0 2 0 0 (x , y) ;
(R
X
'
R ) (yz, zx)
y
x andy are taken along 2C ~ ; C'
2
and C ~ ' act in the xy plane.
D E 2C 2C
SCi
< = 72° h = 10
5 5 5 2
A 1 1 1 1
2 2 2
Z ; X +y
1
A 1 1 1 1 z' R
2
,
z
E 2 2cos < 2cos
2< 0 (x , y) ; (R , R ) (yz, zx)
1 x y
2 2
E 2 2cos 2< 2cos
c
0 (x y xy)
2
,
D
6
E 2C 2C C 3C
'
3C' I h = 12
6 3 2 2 2
2 2 2
A 1 1 1 1 1 1
z ; x +y
1
A 1 1 1 1 1 1 z' R
2
,
z
B 1 1 1 1 1 1
1
B 1 1 1 1 1 1
2
E 2 1 1 2 0 0 (x, y) ;
(R
x
'
R ) (yz, zx)
1
y
2 2
xy)
E 2 1 1 2 0 0
(x y ,
2
x, y and (u) are taken along 3C ~ .
326
Groups D
nh
(n = 26)
Appendix 11
DZh
E C (z) C (y) C (x) i a(xy) a(zx) a(yZ) h = 8
222
A 1 1 1 1 1 1 1 1
2 2 2
Z ; x' y ,
9
B 1 1 1 1 1 1

1  1 R xy
19 Z
B 1 1 1 1 1 1 1  1 R zx
2g
Y
B 1 1 1 1 1 1 
1 1 R yz
3g X
A 1 1 1 1 1 1 
1  1
u
B 1 1 1 1 1 1 1 1 z
lu
B 1 1 1 1 1 1

1 1
Y
2u
B 1 1 1 1 1 1 1  1 x
3u ;
D
3h
E 2C 3C
'
ah
25
3a
v h = 12
3 2 3
A' 1 1 1 1 1 1
2 2 2
Z ; X +y
1
A' 1 1 1 1 1 1 R
2
z
E ' 2 1 0 2 1 0 (x , y)
2 2
xy) (x y ,
AI I
1 1 1 1 1 1
1
AI I
1 1 1 1 1 1 z
2
E I I
2 1 0 2 1 0 (R
x'
R
)
(yz, zx)
y
D4h ,
E 2C C 2C
'
2C' I
i 25 ah
2a
v
2a
d
h = 16
4 2 2 2 4
A 1 1 1 1 1 1 1 1 1 1
2 2 2
Z ; X +y
19
A 1 1 1 1 1 1 1 1 1 1 R
2g z
B 1 1 1 1 1 1 1 1 1 1
2 2
19
X y
B 1 1 1 1 1 1 1 1 1 1 xy
2g
E 2 0 2 0 0 2 0 2 0 0 (R
x'
R
) (yz, zx)
9
y
A 1 1 1 1 1 1 1 1 1 1
lu
A 1 1 1 1 1 1 1 1 1 1 z
2u
B 1 1 1 1 1 1 1 1 1 1
lu
B 1 1 1 1 1 1 1 1 1 1
2u
E 2 0 2 0 0 2 0 2 0 0 (x , y)
u
2C
2
' lie in 2a
v
and are also the x andy axes; 2C
2
" lies in 2a
d
_
Appendix 11
327
D E 2C 2C
2
SCi
O"b 25 25
3
50"d
~ =
72°
h = 20
5h 5 5 2 5 5
AI
1 1 1 1 1 1 1 1
2 2 2
Z .
x +y
1
,
AI
1 1 1 1 1 1 1 1 R
2
Z
£1
2 2cos ~ 2cos
2 ~ 0 2 2cos ~ 2cos
2 ~ 0 (x, y)
1
£1
2 2cos 2 ~ 2cos
c
0 2 2cos 2 ~ 2cos
c
0
2 2
2
(x y ,xy)
A I I
1 1 1 1 1 1 1 1
1
AI I
1 1 1 1 1 1 1 1 z
2
£1 I
2 2cos ~ 2cos
2 ~
0 2 2cos ~ 2cos
2 ~ 0
(R
x
'
R ) (yz, ZX)
1
y
£1 I
2 2cos 2 ~ 2cos
~
0 2 2cos 2 ~ 2cos
c
0
2
D
6h
E 2C 2C C 3C
I
3C
I I
i 25 25
O"b 30"d 30"v
h = 12
6 3 2 2 2 3 6
1 1 1 1 1
2 2 2
A 1 1 1 1 1 1 1 z ; x +y
19
A 1 1 1 1 1 1 1 1 1 1 1 1 R
2g Z
B 1 1 1 1 1 1 1 1 1 1 1 1
19
B 1 1 1 1 1 1 1 1 1 1 1 1
2g
£ 2 1 1 2 0 0 2 1 1 2 0 0 (R
x'
R
)
(yz, zx)
19 y
2 2
£ 2 1 1 2 0 0 2 1 1 2 0 0 (x y ; xy)
2g
A 1 1 1 1 1 1 1 1 1 1 1 1
1u
A 1 1 1 1 1 1 1 1 1 1 1 1 z
2u
B 1 1 1 1 1 1 1 1 1 1 1 1
1u
B 1 1 1 1 1 1 1 1 1 1 1 1
2u
t: 2 1 1 2 0 0 2 1 1 2 0 0 (x , y)
1u
£ 2 1 1 2 0 0 2 1 1 2 0 0
2u
C ~ passes through opposite C atoms, and C; bisects opposite CH bonds, or vice
versa; C~ must lie in o, and C; in O"d. Interchange of C~ and C; will
interchange the Big, B
2g
and B
1u
, B
2u
labels.
328 Appendix 11
Groups D
nd
(n = 24)
D
2d
E 25 C 2C' (x) 2ad h = 8
4 2 2
2 2 2
A 1 1 1 1 1 z ; x +y
1
A 1 1 1 1 1 R
2 Z
2 2
B 1 1 1 1 1 x y
1
B 1 1 1 1 1 z xy
2
E 2 0 2 0 0 (x , y) ; (R
x
, R ) (yz, ZX)
y
D
3d
E 2C 3C' i
25 3ad h = 12
3 2 6
A 1 1 1 1 1 1
2 2 2
Z ; x +y
19
A 1 1 1 1 1 1 R
2g
z
1 0 1 0 (R , R )
2 2
xy) ; (yz, ZX)
E 2 2
(x y ,
g
x
Y
A 1 1 1 1 1 1
lu
A 1 1 1 1 1 1 z
2u
E 2 1 0 2 1 0 (x , y)
u
D E 25 2C 25
3
C 4C' 4a
4d 8 4 8 2 2
d
A 1 1 1 1 1 1 1
2 2 2
Z ; X +y
1
A 1 1 1 1 1 1 1 R
2
z
B 1 1 1 1 1 1 1
1
B 1 1 1 1 1 1 1 z
2
E 2 ';2
o ';2
2 0 0 (x, y)
1
E 2 0 2 0 2 0 0
2 2
xy)
2
(X y ;
E 2 ';2 0 ';2
2 0 0 (R , R ) (yz, zx)
3
X y
Cubic groups
E 4C 4C
2
3C
i21l/3
h = 12
T
£: = e
3 3 2
2 2 2
A 1 1 1 1 X +y +z
{
•
}
1 e e 1 2 2 2 2 2
E (X y , 2z X v )
•
1 e e 1
T 3 0 0 1
(x, y, z ) ;
(R
x
'
R, R ) (xy, yz, zx)
y z
Appendix 11 329
i271/3 2 2
T
h
E 4C 4C 3C
i
45 45 3ad
£: = e h = 24
3 3 2 6 6
A 1 1 1 1 1 1 1
2 2 2
1 x +y +z
9
• • 222
E
{
1 c e 1 1 e e
:}
(2z x y ,
9 • •
2 2
1 e e 1 1 e e X y )
T 3 0 0 1 3 0 0 1 (R , R , R ) (xy, yz, zx)
9
x y z
A 1 1 1 1 1 1 1 1
u
• •
E
{
1 e £: 1 1 £: £:
1}
u
• •
1 e e 1 1 £: £: 1
T
3 0 0 1 , 3 0 0 1 (x, z) u y,
T
d
E 8C 3C 65 6ad
h = 24
3 2 4
1 1 1 1
2 2 2
A 1 x +y +z
1
A 1 1 1 1 1
2
222 2 2
E 2 1 2 0 0 (2z x y , x y )
T 3 0 1 1 1 (R , R , R )
1 X
Y
z
T 3 0 1 1 1 (x , y, z) (xy, yz, ZX)
2
0
E 8C 3C 6C 6C' h = 24
3 2 4 2
A 1 1 1 1 1
2 2 2
X +y +z
1
A 1 1 1 1 1
2
222 2 2
E 2 1 2 0 0 (2z x y , x y )
T 3 0 1 1 1 (x , y, z ) ; (R , R, R )
1 X
Y
z
T 3 0 1 1 1 (xy, yz, ZX)
2
330
Appendix 11
~
E 8C 3C 6C 6C
1
i 85 30"h 65 60"d h = 48
3 2 4 2 6 4
1 1 1 1 1 1
2 2 2
A 1 1 1 1 x +y +z
19
A 1 1 1 1 1 1 1 1 1 1
2g
2 2 2
E 2 1 2 a a 2 1 2 a a (2z x y ,
g
2 2
X y
T 3 a 1 1 1 3 a 1 1 1 (R
x'
R
y'
R )
19
Z
T 3 a 1 1 1 3 a 1 1 1 (xy, yz, zx)
2g
A 1 1 1 1 1 1 1 1 1 1
lu
A 1 1 1 1 1 1 1 1 1 1
2u
E 2 1 2 a a 2 1 2 a a
u
T 3 a 1 1 1 3 a 1 1 1 (x , y, z)
lu
T 3 a 1 1 1 3 a 1 1 1
2u
Groups C""v and D"'h
c.,
E
2C4>
oOO"V h = 00
00
A
L+
1 1 1
2 2 2
 Z Z ; x +y
1
A L

1 1 1 R 
2 Z
E  IT 2 2cos
4>
a (x , y) ; (R
x'
R
) (yz, zx)
1 y
E !J. 2 2cos
24>
a (x
2 2
xy)
 y ,
2
E

~ 2 2cos
34>
a
3
Appendix 11
331
D""h
E
2C4>
ooO"v
i 254>
... coG h = 12
00 00
2
A
~ +
1 1 1 1 1 1
2 2 2
 Z ; x +y
1q q
A ~

1 1  1 1 1 1 R
2q q
z
E  IT 2 2cos
4>
0 2 2cos
4>
0 (R , R
) (yz, zx)
1q q
X
Y
E lJ. 2 2cos
24> 0 2 2cos
24>
0
2 2
xy)  (X y ,
2q q
E  4> 2 2cos
34>
0 2 2cos
34> 0
3q q
A 
~ +
1 1 1 1 1 1 z
1u u
A ~

1 1 1 1 1 1 
2u u
E  IT 2 2cos
4>
0 2 2cos
4>
0 (R
x'
R
)
(yz, zx)
1u u y
E lJ. 2 2cos
24>
0 2 24>
0
2 2
xy)  2cos (X y ,
2u u
E  4> 2 2cos
34> 0 2 2cos
34>
0
3u u
Notes to Character Tables
1. In tables that contain complex characters, 8 = exp(i2n/n), written as e
i21t1n
, is
used, and its conjugate 8* = e
i2
"ln: for n = 3 or 6, 8
2
= 8*. From de Moivre's
theorem, we have
8 =exp(i2n/n) = cos(2n/n) + isin(2n/n).
For given values of n certain useful results follow (i = ..Jl):
• •
n e £; +
e £;  e
3 liV3  1)/2 1 i\!J
4 o 12 2i
5 {"Is  1 + i ,,1[2 ("Is + 5)] }/4 ("Is  1) V[ ("Is + 5) 12]
6 liV3  1)/2 1 iV3
8 ,,12(1 + il
,,12 iV2
2. In some groups that involve fivefold symmetry the functions cos(72°) and
cos(l44°) occur. It is often convenient to make use of the following relations, as we
have implicitly in Appendix 9.
332
Appendix 11
2cos(72°) = (l  ;/5)/2 = S
2cos(l44°) = (l + ;/5)/2 = c;,
S2 = I + S
c;,2 = I + c;,
S + c;, = I
sc;, =1
3. In some instances, for example the irreducible representation E
2g
in D
6h
, two
product terms coupled under that symmetry are not on the same normal basis. Thus,
in place of (x
2
 /, xy), we could write ([x
2
 /]/;/2, xy). Generally, we have chosen
to carry out the normalization in conjunction with deriving the SALCs.
4. In certain groups, a change in the orientation of the reference axes with respect
to the symmetry elements of the group may change the functions that span a given
irreducible representation; see under C
2v
, for example.
5. In C
oov
and D
ooh
, the ... represent the symmetry classes 2cos:' , 2cos'.! , ..., with
characters such as and for IT
g
, and so on. In using these groups,
these classes are ignored as the information that they provide is redundant.
Al1.2 CORRELATION TABLES
The correlation tables show how the irreducible representations of a point group are
decomposed into those of its subgroups, contingent upon a reduction in the
symmetry from the given group.
We have shown in Section 6.6 that the construction of a correlation table is a
straightforward process. Thus, we give here a selection of partial correlation tables,
those that we are most likely to meet in chemical problems. Other compilations of
character tables and correlation tables are available in the literaturel'"!
In these tables, a superscript to a subgroup symbol indicates the symmetry axis or
symmetry plane, from the supergroup, that is preserved in the subgroup. Thus, C:"
(under C
2v
) means that the zx plane in C
2v
is the a plane in C.; C (under D
2
0
means that C
2
along z in D
2h
is C
2
in C
2v
; (under C
4v
) means that the ad planes
in C
4v
are the a planes in C
2v
; D (under D
4h
) means that the C in D
4h
are C in
crhH:r(lI.)')
D
2d
; D
2h
(under D
6h
) means that the ah plane of D
6h
becomes the xy plane in
D
2h
, and so on.
In some tables, particularly those of high order, not all of the lower subgroups of
the point groups are recorded; a full list of subgroups is shown by Figure 3.1, from
which further deductions can be made.
In the following correlation tables, for additional clarity, the subgroups have
been given in a slightly different notation from that which we use for point groups
generally, and for the point groups from which the subgroups have been derived.
Appendix 11
333
Groups C
nv
(n =24, 6)
C
2v
2 s s
A A A' A'
1
A A
A' ,
A"
2
B B A'
A' ,
1
B B
A' ,
A'
2
C
3v
3 s
A A
A'
1
A A
A' ,
2
E E
A' + A"
C
4v
2v 2v 2 s s
A A A A A A'
A' ,
1 1 1
A A A A A A"
A' ,
2 2 2
B B A A A A'
A' ,
1 1 2
B B A A A
A' ,
A'
2 2 1
E E B + B B + B 2B A' + A" A + A"
1 2 1 2
(J'V')(J' (ZX)
C
6v
6 3v 3v 2v 2v 3 s s
A A A A A A A A' A'
1 1 1 1
A A A A A A A
A' , A' ,
2 2 2 2
B B A A B A B A'
A' ,
1 1 2 1
B B A A B A B
A' ,
A'
2 2 1 2
E E E E B + B E 2B A'+
A' ,
A'+
A' ,
1 1 1 2
E E E E A + A E 2A A' +
A' ,
A' +
A' ,
2 2 1 2
334
Appendix 11
Groups C
nvh
(n =24)
C
2h
t;> t;> t;>.
2 s 1
A A
AI
A
9 9
B B
AI I
A
9 9
A A
A I I
A
u u
B B
AI
A
U u
C
3h
t;> t;>
3 S
AI
A
AI
E
'
E 2A
'
AI I
A
AI I
E' I
E
2A' I
C
4h
t;> !I
t;> t;> t;> t;>.
4 4 2h 2 s 1
A A A A A
AI
A
9 9
9
B B B A A
AI
A
9
9
9
E E E 2B 2B 2A
'
2A
9 9
9
A A B A A
AI I
A
u u
u
B B A A A
AI I
A
u u
u
E E E 2B 2B 2A
'
2A
u u
u
Groups D
nvh
(n =24, 6)
D
2h V
t;>z t;>Y t;>x t;>z t;>Y t;>x t;>z t;>Y t;>x
t;>xy t;>zx t;>Yz
2 2v 2v 2v 2h 2h 2h 2 2 2 s s s
A A A A A A A A A A A
AI AI AI
9
1 1 1
9 9 9
B B A B B A B B A B B
AI
AI I A I I
19
1 2 2 1
9 9 9
B B B A B B A B B A B
AI I AI AI I
2g 2 1 2 2
9 9 9
B B B B A B B A B B A
AI I AI I AI
3g 3 2 1 2
9 9 9
A A A A A A A A A A A
AI I AI I AI I
U 2 2 2 u u u
B B A B B A B B A B B
A I I AI AI
1u 1 1 1 2 u u u
B B B A B B A B B A B
AI AI I
AI
2u 2 2 1 1 u u u
B B B B A B B A B B A
AI AI AI I
3u 3 1 2 1 u u u
Appendix 11 335
lTh7lT'v
t;'lTh
D
3h
t;'
'J)
t;' t;'
t;'3
t;'
t;'lTV
3h 3 3v 2v 2 s s
A' A' A A A A A A' A'
1 1 1 1
A' A' A A B A B A'
A' ,
2 2 2 2
£' £' t: e A + B t: A + B 2A' A' + A"
1 2
A' , A' ,
A A A A A
A' , A' ,
1 1 2 2
A' , A' ,
A A B A B
A' ,
A'
2 2 1 1
E.' , E' ,
£ t: A + B s A + B
2A' ,
A' + A"
2 1
'J)
C2' C2"
t;'
C2' C2"
t;' !f
D
4h
'J) 'J) t;' 'J) 'J)
4 2d 2d 4v 4 h 2h 2h 4 4
A A A A A A A A A A
19 1 1 1 1 g g g
A A A A A A B B A A
2g 2 2 2 2 g 19 19
B B B B B B A B B B
19 1 1 2 1 g g 19
B B B B B B B A B B
2g 2 2 1 2 g
19
g
£ £ t: e e t: B + B B + B t: e
g g 2g 3g 2g 3g
A A B B A A A A A B
lu 1 1 1 2 u u u
A A B B A A B B A B
2u 2 2 2 1 u lu lu
B B A A B B A B B A
lu 1 1 2 2 u u lu
B B A A B B B A B A
2u 2 2 1 1 u lu u
£ e t: t: s £ B + B B + B £ £
u u 2u 3u 2u 3u
336
Appendix 11
O'v'HJ" (yz)
O'h7O' t xy)
bO'h
D6h
en en en b b b b b
6 3h 2h 3h 3 2v 2v 2 s
A A A' A A' A A A A A'
19 1 1
9
1 1 1
9
A A A' B A' A B B A A'
2g 2 2 19 2 1 1
9
B B
A' ,
B
A' ,
A A B B
A' ,
19
1 1 2g 2 2 2
9
B B
A' ,
B
A' ,
A B A B
A' ,
2g 2 2 3g 1 2 2
9
£ £
E.' ,
B + B
E' ,
£ A + B A + B 2B
2A' ,
19 1 2g 3g 2 2 2 2
9
£ £ £' A + B £' £ A + B A + B 2A 2A'
2g 2
9 19 1 1 1 1
9
A A
A' ,
A
A' ,
A A A A
A' ,
1u 1 1 u 2 2 2 u
A A
A' ,
B A" A B B A
A' ,
2u 2 2 1u 1 2 2 u
B B A' B A' A A B B A'
1u 1 1 2u 1 1 1 u
B B A' B A' A B A B A'
2u 2 2 3u 2 1 1 u
£ £ £' B + B £' £ A + B A + B 2B 2A'
1u 1 2u 3u 1 1 1 1 u
£ £
E.' ,
A + B
E.' ,
£ A + B A + B 2A
2A' ,
2u 2 u 1u 2 2 2 2 u
Groups D2d, J
d
andOh
C 7C (z )
2 2
C2'
D
2d
!I en b b
2
b b
2 2v 2 s
A A A A A A A'
1 1
A A B A A B
A' ,
2 1 2
B B A A A A
A' ,
1 2
B B B A A B A'
2 1 1
£ £ B + B B + B 2B A + B A'+
A' ,
2 3 1 2
1" I
en b
5.,
en b b b b
2d 3v 2 2v 3 2 s
A A A A A A A A A'
1 1 1 1
A B A B A A A A
A' ,
2 1 2 2
£ A + B £ A + B 2A A + A £ 2A A'+ A"
1 1 1 2
T A + £ A + £ A + £ B +B +B A +B +B A + £
A + 2B A'+ 2A"
1 2 2 1 2 3 2 1 2
T B + £ A + £ B + £ B +B +B A +B +B A + £
A + 2B 2A'+ A"
2 2 1 1 2 3 1 1 2
Appendix 11
337
0.,1
o ':J
1) 1)
b b
1)
b
d 4h 2d 4v 2v 3d 2h
A A A A A A A A A
19 1 1
19
1 1 1 19
9
A A A B B B A A B
2g 2 2
19
1 1 2 2g
9
E E E A + B A + B A + B A + A E A + B
9
19 19
1 1 1 1 1 2
9 9 9
T T T A + E A + E A + E A + B + B A + E A + 2B
19 1 1 2g
9
2 2 2 1 2 2g
9 9 9
T T T B + E B + E B + E A + B + B A + E 2A + B
2g 2 2 2g
9
2 2 1 1 2 19 9 9 9
A A A A B A A A A
1u 1 2 1u 1 2 2 1u u
A A A B A B A A B
2u 2 1 1u 1 2 1 2u u
E E E A + B A + B A + B A + A E A + B
u 1u 1u 1 1 2 2 1 2 u u u
T T T A + E B + E A + E A + B + B A + E A + 2B
1u 1 2 2u u 2 1 1 1 2 2u u u u
T T T B + E A + E B + E A + B + B A + E 2A + B
2u 2 1 2u u 2 1 2 1 2 1u u u u
All.3 MULTIPLICATION PROPERTIES OF IRREDUCmLE
REPRESENTATIONS
We consider here how the direct products of irreducible representations give rise to
other irreducible representations or their sums.
General rules
A@A=B@B=A; A@B=B; A@E=B@E=E;
A @ T = B @ T = T; g @ g = u @ u = g; g @ u = u;
'(8)'="(8)"='; '(8)"='.
Subscripts on A and B
1 @ 1 = 2 @ 2 = 1; 1 e 2 = 2; (except for O
2
and 0
2
0
For B representations in O
2
and 02h: 1 @ 2 = 3; 2 @ 3 = 1; 3 @ 1 = 2.
Doublydegenerate representations
For C
3
, C
3v
, C
31b
0
3,
031b 03d, C
6
, C
6v
, C6!b 0
6,
06h, 56, 0, 0." T, T
Ib
T
d
:
EI@EI=E2@E2=AI +A
2+E2
; E
I
@E
2=BI
+B
2+EI.
For C4, C4v, 02d, 0
4,
041b 54:
E@E=A
I
+A
2+BI
+B
2.
Where groups have symbols A, B and E (without subscripts) read Al =A
2
=A, and
soon.
Triplydegenerate representations
For Td, 0, 0.,:
E @ T
I
= E @ T
2
= T
I
+ T
2;
T
I
@ T
I
= T
2
@ T
2
= AI +E + T
I
+ T
2
;
T
I
@ T
2
= A
2
+E + T
I
+ T
2
.
338
Appendix 11
Linear groups (C""v, D",,0
L+ 0 L+ = L 0 L =L+; L+ 0 L ": L;
L+ 0 Il =L 0 Il =Il; L+ 0 ~ = L ~ 0 ~ = ~ ;
Il 0 Il = L+ + L + ~ ; ~ 0 ~ = L+ 0 L + I';
n 0 ~ = Il + <1>;
In all cases, a check may be made by forming the direct product of the irreducible
representations for the point group under consideration. For example, in Oru the
above rules show that E
g
0 T
l u
= T
l u
+ T
2u
. In extenso, we have:
Oh
E 8C 3C 6C 6C'
i
85 3a
h
65 6a
d
3 2 4 2 6 4
E 2 1 2 0 0 2 1 2 0 0
g
T 3 0 1 1 1 3 0 1 1 1
1u
E ® T 6 0 2 0 0 6 0 2 0 0
g 1u
which confirms that E
g
0 Ti« = Ti« + T
2u
•
Direct products of spin multiplicities
For a summary and examples of this topic, the reader is referred to Section 7.6.1.
Appendix 12
Study aids on the internet
A12.1 COMPUTER PROGRAMS
Within this book, the reader is referred to programs that have been designed to
assist in gaining the desired familiarity with the subject matter of the book.
The programs have been written in a selfcontained and selfexplanatory manner.
They may be executed on any IBMcompatible computer operating under DOS or
WINDOWS, and need only a monitor and a printer as peripherals. The word in
parentheses after the title of each program listed is its calling name; thus, the
program on the Euler combination of rotations is called by EULS (or EULH in the
HermannMauguin symmetry notation). The information on the monitor guides the
user through each program. Access to the programs is through Worldwide Web
address www.honvood.nct/puhlish from where further instructions are available.
Programs
The programs available are listed below; in some cases, test data are provided in
order to demonstrate the correct working of the program.
Eigenvalues and eigenvectors (EIGN).
Huckel molecularorbital calculations (HUCK).
Pointgroup derivation (EULS in the Schonflies notation, and EULH in the
HermannMauguin notation).
Pointgroup recognition (SYMS in the Schonflies notation, and SYMH in the
HermannMauguin notation).
Roots of polynomials (POLY).
Curve fitting and interpolation (INTP).
Reduction of representations: D
6h
, (RD6H): D
4h
, (RD4H).
(RD6H is supplied also in FORTRAN77 source code (RD6H.FOR) so that a reader
familiar with FORTRAN77 may modify it for other point groups. The author cannot
undertake to check any such modlfications.y
Figure A12.1 is a block diagram of the scheme embodied in the pointgroup
recognition program SYMS (and SYMH). The program accommodates the 32
crystallographic point groups, and the linear groups C",v and D
coh
, which fit the
scheme under types (11) and (IV), respectively. In this scheme n refers to the degree
of proper rotation, as in C, and N refers to the number of these C
n
axes. Table AU.I
compares the Schonflies and HermannMauguin pointgroup symmetry symbols.
340 Appendix 12
Table AU.l Schonflies and HermannMauguin symmetry notations
Schonflies HermannMauguin Schonflies Hermann Mauguin
C
1
1
D
2
222
C
2
2 D
3
32
C
3
3
D
4
422
C4
4
D
6
622
C
6
6
D
2h
mmm
Cj I
D
3h
6m2
(2)
4
C, (51)
m
D
4h
mm
m
4
6
54
D
6h
mm
m
56
3
D2d
42m
C
2h
2/m
D
3d
3m
C
3h
(53)
6
T
23
C
4h
4/m
T
h
m3
C
6h
6/m
T
rl
43m
C
2v
mm2 0 432
C
3v
3m
Oh
m3m
C
4v
4mm
c.,
oom
C
6v
6mm
DOllh
oo/m
Table A12.2 contains the key to the relationship between the model number and
point group inthe pointgroup recognition programs.
rn fill (JII) (IV)
t::
= c:.
....
N
Y.. No r:;:l
.
51
I
Yeo
n
Y.. Gl? No [.g
> ..
h n 3d
Yo,
[16 'l::>'", J
Y"
e
nh
'OOf
[sJ
'e, >10 I
'h
>1 e, I
(1 J. c ,I
h n
N" f
1
0
2. I
>Je,hl
>1 T,,!
[n No
Y"L_
r
n
0 J I
ves
lind .
H > 11
.
Y",>[
1 Cn?
N,t
r
 ·_·.... ·... 1 '0' CF 1. C ?
h n
Nol
Yo, No r:;:l
+ n '" 4? io
Y..
o
Fig. A12.1 Blockdiagram for pointgroup recognition program,
w

342 Appendix 12
Table A12.2 Model numbers and point groups for the pointgroup recognition
program
Model numberls Point group Model numberls Point Group
115 m3m 7275 21m
16 mm2 76 mm2
1721 43m 77 2
2225 m3 7879 1
26 432 80 21m
27 23 81 6mm
28 43m 82 1
2935
6
83 mm m
m
36 622 84 3
37 61m 85 4
3841 3m 86 4
42 3m 87 4mm
43 32 88 6
4446 6m2 89 "6
47 32 90 6m2
48 :3 91 1
4954
4
92 mm m
m
55 422 93 3
56 41m 94 4
5757 42m 95 4
5963 mmm 96 4mm
64 mm2 97 6
6566 mmm 98 6
67 222 99 m
6870 21m 100 4mm
71 mm2 101 oom
102 oolm
Appendix 13
Some useful rotation matrices
We list matrices for some of the less familiar symmetry operations. Mostly, they
refer to threefold, fourfold and sixfold positive (anticlockwise) rotations in different
orientations; the orientations are given in terms of directions [UVW], with respect to
crystallographic axes.
Twofold symmetry
[
0 1 0
] [
a a 1
]
n
0 a
]
1 0 a
a 1 a
a 1
a a 1 1 a a 1 a
2 (C ) 2
(C ) 2 (C )
2
2
2
along [l10]
along [10l)
along [all
   
For the orientations [11 0], [1 () 1] and (01 1 ], all signs must be negative. For 2
(8
1
) along the same directions, or m (0') normal to them, negate all signs of a given
appropriate matrix.
Threefold symmetry along <111>
1
a
a
3 (C ) along
3
along [111]
3 (C ) along
3
along (111]
3 (C ) along
3
along [l1l)
3 (C ) along
3
along [111]
For 3
2
(C; ), form the product 33. For 3 (S ~ ) and 3
5
(S6), negate all signs in the
matrices for 3 and 3
2
, respectively.
Threefold symmetry along (0(1*I) (hexagonal system)
1
1
[:
1
1
a
3 (C )
3
~ ]
~ ]
a 1
3 (S5)
6
344
AIJI)cndix 13
The asterisk in [00*1] corresponds to an intercept of zero on the hexagonal axis u,
but it does not arise in the matrix itself.
For 3
2
(C; ), form the product 33, and for 3
5
(S6), negate all signs in the matrix
for 3
2
• 3 (C
3
) == 3
4
(S ~ ); 3
2
(C ; ) == 3
2
(S :); 3
3
(8 ~ ) = i (i)
Fourfold symmetry
[
1
a
J
H
1 a
]
a a
a a
a 1
a 1
4 (C )
4
(S3)
4
4
along [001]
along [001]
For 4
3(C
~ ) and 4: 3 (S4) form the inverses of the matrices for 4 and 4:, respectively.
6 (C )
6
along [001]
Sixfold symmetry
[
 1
1
a : ~ ]
6 (S5)
3
along [001]
~ ]
1
a
a
[
Note that 6 == 23
2
, 6

233 and 23 == 6
1
: the position of the operator 2 is
immaterial here.
6
2
(C
2
)

3
rc ). 6
3
(C
3
)
=2
rc ). 6
4
(C
4
)

3
2
(C
2
) .
6 3 ' 6 2 ' 6 3 '
6
2
(S4)

3 (c I: 6
3
(S3)
= m (o) ; 6
4
(S2)

3
2
(C
2
) .
3 3 ' 3 3 3

Point group 6, equivalent to C
3h
, is allocated to the hexagonal crystal system
because 6 cannot operate on a rhombohedral lattice. Matrices other than those
listed above are either selfevident or are obtainable readily from those given here or
elsewhere in the text.
A useful matrix for an anticlockwise rotation ~ about the z axis, normal to the xy
plane, where xl\y = y is given by
Appendix 13
345
sin(q» ]
sine',)')
[ COS(q»
[
sin(q»cos(',)')
sine',)')
] [
• (A.) • ( ) Sin(q»COs
2(',)')]
0
SIn 'I' SIn ',)'  . ( )
SIn ',)'
[
(
A.) Sin(q»COS(',)')] 0
cos 'I' + • ( )
SIn ',)'
o o 1
For ~ =60° and y = 120°, the matrix becomes
1
o
o
which is the matrix given above for a 60° rotation about [00*1].
Appendix 14
Apologia for a single symmetry notation
Students meeting symmetry for the first time are generally taught crystallography in
the HermannMauguin notation, and spectroscopy and theoretical chemistry in the
Schonflies notation, and sometimes both at the same stage in a degree course. These
uses of the two notations are traditional. However, it is the author's view that a
single symmetry notation could suffice for all purposes. Some indication of this view
will have appeared in Chapter 8 and Appendix 13, and the purpose ofthis Appendix
is to elaborate the the idea of a single symmetry notation.
Pointgroup symmetry may be addressed equally well in both notations: there is
little to choose between the designations D
2h
and mmm. However, if we compare the
equivalent spacegroup symbols D~ ~ , and Pbcn, it is clear that the latter, Hermann
Mauguin, notation is superior, because it indicates the nature of the symmetry
planes present and their relative orientation, within the meaning of the symbol (see
Sections 8.3 and 8.6ft). Hence, is it contended that a single symmetry notation
should be based on the HermannMauguin system.
Certain minor adjustments would need to be made to the HermannMauguin
pointgroup symbols to achieve comparability with the Schonflies notation. They are
the following:
21m 2 along z, with m as the xy plane; the International Tables
(7
) already
provides for this setting.
mm2 Change to 2mm, so that the first position in the symbol refers to the z axis,
as with other point group symbols; changes to some spacegroup symbols
would follow:
6 m2 Change to 6 2m, so that the diads are in the second position of the symbol,
as with 4 2m; changes in some some spacegroup symbols would follow.
In discussing symmetry operations or symmetry operators, the HermannMauguin
symbols would be written in bold type, to distinguish them from symmetry elements,
with multiplying factors for symnmetry classes in italics. Some of the effects of
these changes may be seen from the following examples, showing a group
multiplication table and a character table for 3m (C
3v
) . They may be compared with
the equivalent tables given in Chapter 3 and, more fully, in Appendix 11.
Appendix 14
3m 1 3 3
2
m m'
m' ,
1 1 3 3
2
m m'
m' r
3 3 3
2
1 m'
m' ,
m
3
2
3
2
1 3
m' ,
m m'
m m
m' ,
m' 1 3
2
3
m' m' m
m' ,
3 1 3
2
m' , m' ,
m' m 3
2
3 1
347
3m 1 23 3m
A 1 1 1
1
A 1 1 1
2
E 2 1 a
Similarly, other familiar group operations can be recast with HermannMauguin
symbols. For example, the similarity transformation of 3 by 3
2
could be written as
(3
2
)" 1
33
2 = (3
2
)" 1
1
= (3
2
)" 1 = 3
These comments are offered firstly to those engaged in the teaching of symmetry,
for it seems likely that the impetus for change would arise from this sector.
Tutorial solutions
SOLUTIONS 1
1.1 Study Sections 1.1 and 1.2.
Threefold (120°) rotational symmetry about the centre of each emblem. Reflection
symmetry in each arm of the MercedesBenz insignia.
1.2 Study Sections 1.1 and 1.2.
(a) one vertical crplane passing through the handle;
(b) two vertical, perpendicular c planes, with twofold (180°) rotational symmetry
about their line of intersection;
(c) infinity rotation about the tumbler axis, with an infinite number of cr planes, all
containing this axis;
(d) as for (b);
(e) as for (c);
(f) three mutually perpendicular o planes, with directions of twofold rotational
symmetry normal to each plane;
(g) as for (c), but with an additional o plane normal to the direction of the infinity
rotation;
(h) no symmetry, because all faces are different;
(i) as for (a);
(j) fivefold (72
0
) rotational symmetry through the centre ofthe flower; five cr planes
through the petals; five o planes between the petals.
1.3 Study Sections 1.1 and 1.2.
(a) 0 B
OA =OB,
AOB = 90
0
•
o
(bl)
A·
OA =OB.
The value of AOB depends on the ratio ofthe sides of the brick.
(b2) o B
OA =OB,
AOB= 90°.
More symmetry revealed, but not a mnumum number of points. Other, less
satisfactory, results exist for both patterns.
1.4. Study Section 1.3.
.!..n.
2
Tutorial Solutions
1.5 Study Section 1.3.
(a) odd; (b) even; (c) even; (d) odd.fe) even.
1.6 Study Sections 1.1 and 1.2.
F, G, J, P, Q, R.
SOLUTIONS 2
2.1 Study Section 2.2.
(a) D(x
3
) + D[sin(x)] = 3x
2
+ cos(x).
(b) L[x + exp(ax)] = In[x + exp(ax»).
(c) D
2
(Ja2) + D
2
(x) = 2k.
(d) X(ax
2
) + D(ax
2
) = ax
4
+ 2ax.
(e) (DX)D(x
2
+ 1) = D[X(2x)] = D(2x
3
) = 6x
2
.
(f) D[X(x
3
») + D[D(x
3
») = D(x
5
) + D(3x
2
) = 5x
4
+ 6x.
349
2.2 Study Section 2.5.1.
rAB=(XA  xB)i + (YA  YB).i + (ZA  zB)k. For (a), rAB =0.298 nm. In (b) the cross term
in rAB.rAE [involving cos(P)] is now nonzero, and rAE = 0.240 nm.
2.3 Study Section 2.4.
(a) Asymmetric Dissymetric
Only Figure 2.6 Only Figure 1.1
(b) Threefold rotational symmetry only. (Twodimensional operations take place
strictly in the plane.)
2.4 Study Section 2.2.
(a) cry plane passing through the handle;
(b) two perpendicular cry planes, intersecting in a (vertical) C
2
axis through the
centre of the table:
(c) C; axis along the length. and an infinite number of cr. planes intersecting in the
Coo axis;
(f) three mutually perpendicular o planes, with a C
2
axis normal to each plane;
(g) as for (c), but with a cr" plane, normal to the C", axis;
(h) C
1
, or identity symmetry only.
2.5 Study Section 2.2.
(a) i at the intersection of C
2
and cr,,;
(b) second cr. plane, perpendicular to the first, with two C
2
axes, normal to S4 and
midway between the cr. planes;
(c) S6 axis coincident with the C
3
axis;
(d) two more C
2
axes, perpendicular to the S6 axis, at 120
0
from the first, and three
cr. planes, intersecting in the 8
6
axis and lying midway between the C
2
axes.
2.6 Study Section 2.3.
(a) z (C
6
axis) perpendicular to the molecular plane; Y in the molecular plane (cr0,
passing through a CH group; x perpendicular to Y, z;
(b) Z (C
2
axis) in the molecular plane, passing through the oxygen atom; y in the
molecular plane, perpendicular to z and passing through the oxygen atom; x
perpendicular to y, z:
350
Tutorial Solutions
~ ]
(c) x, y and z pass through C and bisect HCH angles (see Example 6.1; x, y and z
are normal to the faces of the surrounding cube);
(d) z (C
2
axis) along the C=C bond; y in the molecular plane, perpendicular to z and
passing through C; x perpendicular to y, z;
(e) z (C
2
axis) normal to the molecular plane, passing midway through the C=C
bond; y lies along C=C, perpendicular to z; x perpendicular to y, z.
(t) None, other than identity.
(g) As (t). Only this compound can show optical activity.
2.7 Study Section 2.5.3.
H
1 7
];
[
0 7 5
];
(a) A + B
=
15 6 (b) A  B
=
11 5 10
3 6
1 3 2
(c) X(B) =16; (d) det(A) = 2
~ e ~ ( : ~
6
~ ) ;
(f)
(19
19
8)
(g)
H
3
112]
4
AB= 32 32
1: ;
AI
=
2 1/2 .
1
2 6
0 1/2
2.8 Study Section 2.5.4.
Most simply, the matrix can be factored:
[
5 2 3
M= 2';3 1
o 0
For the 1 x 1 matrix, the eigenvalue is 1, with an eigenvector of (1). For the 2 x 2
matrix, 28 = 60°, from (2.59). Hence, for Ie = 7 the eigenvector is(J312 ) . for Ie =1
1/2 '
h
. . ( 1/2) ( 1/2) (112)
t e eigenvector IS r: . Remember that r: may bewritten as r: .
\/3 12 \/3 12 \/3 12
2.9 Study Section 2.5.3.
C r r'
R = ( ~
0
~ ] , = (!
1
~ ] ,
Gv(zx) ;
1 whence
R1C
R 0
0
0
which represents the operation C ~ .
Tutorial Solutions 351
2.10 Study Sections 2.5.3 and 2.5.5.
(a)B=A (b)B=A*
(c) B = A (d) B = At
(e) B =k
l
(f) B =AI =A(A is orthogonal)
2.11 Study Section 2.5.1.
(a) Let the cube be defined by the orthogonal vectors a, b and c, where a = b = c.
Two facediagonals d, and d
2
make an angle 8 at the origin. Then, we have
d =
1
a + c; d = b + c. Thus, cas(S)
2
c)· (b + c) = c2/(cV2
c
2)V(b2
+ c
2)
= (d ·d )/d d =
1 2 1 2
cv2) = 1/2; S = 60°.
(b) In a similar manner, d
l
=a + b + c; d
2
=c; cos(8) = 11"3; 8 =54.74°.
(c) Following the procedure in (b), cos(8) = (a+bic).', but a =b 7: c. Thus, cos(8) =
dZdZ
c
2/Id(2a2
+ c
2
) ] = III"(2a
2
/c2 + I)] =3/"17 =0.7276; 8 =43.31°.
2.12 Study Section 2.5.4.
Following Example 2.7, we diagonalize the 2 x 2 matrix ( ~  ~ ) ; it is not
symmetric. The characteristic equation is ,,} + I = 0; thus the eigenvalues are ±i.
For A. = +i the eigenvector is G); for A. = 1, (j. The complete eigenvectors are
[:J and (l the diagonalizing matrix ois [; .: !J, and g" is [: ~ : ',;"l
Hence, the similarity transformation Q
1AQ
produces the required diagonal matrix,
(
. 0 OJ
namely, o 1 0 .
o 0 1
SOLUTIONS 3
3.1 Study Sections 3.2.2 and 2.5.3.
C
2
commutes with a; E commutes with all other symmetry operators.
3.2 Study Section 3.2.3.
(a) ~ h E C
2
i (Tb
E E C
2
i (Tb
C
2
C
2
E (J"b i
i i (Tb E C
2
(Tb (Tb i C
2
E
352
Tutorial Solutions
(b) E S
S3
C C
I
CI I
O"d
0"'
02d
d
4 4 2 2 2
E E S
S3
C C
I
CI I
O"d
O"d'
4 4 2 2 2
S S C E
S3
O"d
0"'
CI I
C
I
d
4 4 2 4 2 2
S3 S3
E C S 0"'
O"d
C
I
CI I
4 4 2 4
d
2 2
C C
S3
S E
CI I
C
I
O"d'
O"d
2 2 4 4 2 2
C
I
C
I
0"'
O"d
CI I
E C
S3
S
2 2
d
2 2 4 4
CII CI I
O"d
0"'
C
I
C E S
S3
2 2
d
2 2 4 4
O"d
O"d
C
I
CI I
O"d' S
S3
E C
2 2 4 4 2
0"'
O"d'
CI I
C
I
O"d
S3
S C E
d
2 2 4 4 2
Czh is Abelian.
3.3 Study Section 3.2.3.
E R R
2
R
3
E E R R
R
R R R
2
R
3
E
R
2
R
2
R
3
E R
R
3
R
3
E R R
2
R= (R
2
r
1
3.4 Study Section 3.2.3.
(a) 0
3
.
(b)
c
2
0
3
E C
C C
I
CI I
3 3 2 2 2
E E C c
2
C C
I
CI I
3 3 2 2 2
C C c
2
E C
I
CII
C
3 3 3 2 2 2
c
2
c
2
E C
CI I
C C
I
3 3
3 2 2 2
C C
CI I
C
I
E c
2
C
2 2 2 2
3 3
C
I
C
I
C
CI I
C E c
2
2 2 2 2 3
3
CI I CI I
C
I
C c
2
C E
2 2 2 2 3 3
Tutorial Solutions
353
(c) C
3
, ~ and c..
(d) Deleting C
2
in the table requires the deletion of C ~ and C ~ ' , leaving C
3
.
Deleting C
3
requires the deletion of C ~ , and two of the C
2
operations, leaving ~ .
The three subgroups are invariant with respect to D
3
.
3.5 Study Section 3.2.5.
By similarity transformations:
E·lavE = o;
C
3
·
l
a
vC3
= a ~
(C i r'e,c ~ = a ~
a ~ l ava
v
= c,
a ~ .lava v = a ~
a ~ .lava ~ = a ~
Hence, ov, a ~ and a ~ belong to the same synunetry class. Alternatively, either
from the action of C
3
or by inspection of a stereogram for D
3
, it is evident that av,
a ~ and a ~ belong to the same class because they are equivalent under C
3
; this
feature is inherent in the second and third of the similarity transformations above.
3.6 Study Sections 3.2.4 and 3.2.5.
e'
2
e' ,
2
e
2
e' ,
2
e'
2
e'
2
e'
2
e'
2
E
e'
2
e
2
e
2
e'
2
E
e
3
e'
2
E
e
3
e' e c e E
2 2 2 3
e
2
E
E
e'
2
e
2
E
5 e
4 2
E 5
4
5 e
4 2
e 53
2 4
53 E
4
E 5
4
E 5
4
E
5
4
e" e' e' e e
2
e E
2 2 2 2 3 3
In 54, deletion of anyone of the operations 8
4
, C
2
or 8 ~ requires the simultaneous
deletion of the other two, leaving the identity group C
l
. Thus, the group 54 cannot be
produced by any combination of synunetry operators other than E and S4. In 56,
deletion of C
3
requires the deletion of C ~ , 8 gand 8
6
, leaving the group Cj •
Deletion of i requires the deletion also of 8 ~ and 8
6
, leaving the group C
3
. Thus,
iC
3
(= C
3
i) = 8
6
. (The subgroups C
3
and Cj are invariant with respect to 56.)
354
3.7 Study Section 3.3.13.3.2.
(a) D
4h
; (b) C
4v
; (c) C
2h
.
3.8 Study Section 3.3.13.3.2.
Tutorial Solutions
x axis y axis z axis Point group
C C C
D
4
}
2 2 4
S S C C
4v
1 1 4
C S S D
2d
2 1 4
3.9 Study Section 3.3.1. and Appendix 3.
+i
~
Fig. S3.1 iC
4v
~ D
4h
The combination with i involves adding the inversion of each point in C
4v
. This
procedure leads to additional symmetry elements: three C
2
normal to C
4
, and O'h
(normal to C
4
) ; see Figure S3.1.
3.10 Study Section 3.3.4.
(a) C
3h
(b) C
2v
(c) D
3d
(d) r, (e) D
4d
mo,
3.11 Study Sections 3.2.13.2.3.
If we assume that the relations AC = D and BC = D hold, then it would follow that
the member D appears twice in the coloumn headed C in the group multiplication
table. Rightmultiplication by C
l
leads to ACC
I
= DC
I
= A, and BCC
I
= DC
l
= B.
Since DC
I
is also uniquely defined, A = B. But this is contrary to the given
conditions; hence, D cannot appear twice in the 'C' column of the table. A similar
argument can be applied to any column or any row in a group of any order.
3.12 Study Sections 3.2.13.2.3.
Leftmultiplication by yl gives ylp = E = ylQ.lpQ = (QPr1pQ. Further, left
multiplication by (QP) gives (QP)ylp =QP =(QP)(QPr1pQ =PQ. Hence, P and Q
commute.
3.13 Study Sections 3.2.13.2.3
(a) 6 I {E A A
2
A
3
} . A
4
= E'
4 " " •
Tutorial Solutions
E A A
2
A
3
E E A A
2
A
3
A A A
2
A
3
E
A
2
A
2
A
3
E A
A
3
A
3
E A A
2
355
Cyclic group; Abelian; only A
2
is its own inverse.
(b) 6 a{E, A, B, C}. Assume that two members, A and B, are their own inverses:
then, C must be its own inverse, because no row or column may contain identical
members:
E ABC
E E ABC
A A E C B
B BeE A
C C B A E
Abstract group; Abelian; no other group of order 4 is possible.
(c) 6
s{E,
A, A
2
, A
3
, A
4
} ; AS = E:
E A A
2
A
3
A
4
E E A A
2
A
3
A
4
A A A
2
A
3
A
4
E
A
2
A
2
A
3
A
4
E A
A
3
A
3
A
4
E A A
2
A
4
A
4
E A A
2
A
3
Cyclic group; Abelian; no member is its own inverse; there is no other group of
order 5.
3.14 Study Sections 3.2.13.2.3.
Point group D
3
. From similarity transformations, or otherwise, C
3
and C ~ are
conjugate to each other, and the three C; are mutually conjugate.
3.15 Study Sections 3.3.1 and 3.3.2.
All except (f) are true.
3.16 Study Section 3.3.1 and Problem 3.6.
While S4 = O'hC4 is true, the equation implies that these three operations belong to a
group of at least order 8: {E, C
4,
C
2
, C ~ , O'h, ...}. The remaining members of this
356
Tutorial Solutions
group would be S4, S ~ and i, that is, C
4h.
The group S4 itself cannot be formed by
the product of any other groups or operations.
3.17 Study Section 3.3.2.
From the symbol we write D
4h
{E, C
4,
C
2,
C ~ , C ~ (Y), C ~ (x), C ~ ' (x,x), C ~ ' (x,x),
CTb, ...}. (Any point on C ~ ' (x,x) has equal coordinates, x.) We know that iC2 = a;
hence, there will be 2ay, operating normally to 2C ~ , and 2ad, operating normally to
2 C ~ ' . Also, we have abC4 = S4 and ahC ~ = S ~ . Assembling these results into
symmetry classes: D
4h{E,
2C
4,
C
2,
2C ~ , 2C ~ , i, 2S
4,
ah , 2av , 2ad}' The group
order is 16, and the group multiplication table would show that it is complete with
these operations. From the symbol we could also draw a stereogram, insert the given
Fig. 83.2 Stereogram drawn from the symbol D4h: C
4
••• C2 is normal to the stereogram and
the thick perimeter line indicates the symmetry plane O"h; halfcircles represent C ~ and C ~
axes.
symmetry elements and repeat a single point, in a general posinon, by the
operations associated with the elements, Figure S3.2. We then see that the elements
i, 20"y, 2ad and 28
4
have been introduced. In order not to miss a symmetry element,
ask the question "How may I get from anyone point to all other points on the
diagram by a single operation?" Compare your stereogram with that for D
4h
in
Figure 3.11.
3.18 Study Sections 3.2.2 and 3.2.3.
We write the group 6{oo, ... , ma, ..., 2a, a, 0, a, 2a, ..., ma, ..., oo}. It is a
translation group under vector addition and shows the following properties.
Closure: a + 2a =3a or, generally, ma + na =(m + n)a;
Identity: ma +0 = 0 + ma = ma;
Inverse: ma + (ma) = O.
.  6
3.19 Study Section 3.3.4. (a) T
d,
4 3m; (b) C4y, 4mm; (c) D
6h
, mm.
m
3.20 Study Section 3.3.4. (a) D
3d,
:3 m; (b) C2y, mm2; (c) C3y, 3m.
SOLUTIONS 4
4.1 Study Section 4.1.
Using the matrix of (4.3),
Tutorial Solutions 357
[1/2 >/3/2
~ ] ,
n
a
~ ]
D(C ) = /3/2 1/2 D(C') = 1
6 2
a a a 1
D(C )D(C ) = M and D(C )D(C ) = M
2
, where
6 2 1 2 6
[1/2 ';3/2
~ ] ,
[1/2
/3/2
~ l
M = /3/2 1/2 M = /3/2 1/2
1 2
a a 1 a a 1
M
1
represents C
2
30° anticlockwise fromv; M
2
represents C
2
30° clockwise from y,
4.2 Study Sections 4.1 and 3.2.2.
(a) Use the matrix of (4.3) with 8 = 240° (or use twice with with 8 = 120°). (b)
Form D(C
3
) and then obtain its inverse.
4.3 Study Sections 4.1 and 4.4.
The characters of the matrices lead to Cod = I) I I 3. This representation may be
reduced to 3A
1
+A
2
+ 2B
I
+ 3B
2
•
4.4 Study the C
2v
character table.
Translation: A I + B
I
+ B
2
:
Rotation: A
2
+ B
1
+ B
2
:
Al +A
2+2BI
+2B
2
;
hence 1.4] + B
2
correspond to vibrational movements (the number of such vibrations
for a nonlinear triatomic molecule is three).
4.5 Study Section 4.3.
(a)A
2
+ 2B
2
:
(b)A
1
+ 2A
2
+ E:
( c ) A ~ +E";
(d) 1.4
1
+ B
I
+ E;
(e) Big + E
1g
+A
2u
+ E
2
\! :
(f)A
l g
+ E
g
+ T
2g
+ T
2u
.
4.6 Study Sections 4.1, 4.4 and 4.5
[
a a
],
n
a a
],
D(E) = 1 a
D(C ) = 1 a
a 1
2
a 1
n
a a
],
[
1 a a
]
D(,)
= 1 a
D(crIJ
= a 1 a
a 1 a a 1
358
Tutorial Solutions
A partial character table may be written as follows:
C
2h
E C
2 ah
E 1
C
2
X 1 x
1 1
a"
x I
x
(4.64) with the first and second rows:
1 + x + 1 + x = 0,
whence x = 1.
4.7 Study Section 4.4.
f" = 4 0 0 4. This may be reduced to 24
u
+ 2B
g
.
4.8 Study Section 4.2.1 and 4.3, and the character table for C
3
.
For A with itself: .! {(1 x 1) + (l x 1) + (l x In= 1;
3
For A with either E: .! {(l x 1) + (l XI::) + (l x I::*)} = 0;
3
For E with itself: .! {(l x l) + (I:: x 1::*) + (1::* x I::)} = 1.
3
[The product of a character of one irreducible representation with itself is the
character multiplied by its conjugate: the conjugate of 1 is 1, but the conjugate of E,
or exp(i2TC13), is 1::*, or exp(i2TC13), so that EE* =E*I:: = 1; for C
3
(I:: + 1::*) = 1.]
4.9 Study Sections 4.2 and 4.5.
For D
3d
h = 12; the group is centrosymmetric. The rules allow the table to be written
in the form:
D3h
E 2C 3C'
ab
2S
3
3ab
3 2
A 1 1 1 1 1 1
19
A 1 1 1 1 1 1
2g
E 2 a b 2 a b
9
A 1 1 1 1 1 1
1u
A 1 1 1 1 1 1
2u
E 2 a b a b
0
FromA
1g
and s; .2... {( I x I x 2) + (2 x 1 x a) + 3h + (l x 1 x 2) + 1 (2 x 1 x a) +
12
3h} =0; hence, 2a + 3h = 2, 10 which the only sensible solution is a = 1 and b =O.
4.10 Study Sections 4.1 and 4.4.
fred = 3 1 I 3, which reduces to 24
1
+ Ih, which we found from Problem 4.4.
D(E) =
Tutorial Solutions 359
[
J'
D(C,)= [
J'
[
J'
D(a:) = [
J.
No symmetry operation interchanges rand a. Thus, the bond vectors form a 2 x 2
representation and the bond angle an independent 1 x 1 representation; the D
matrices are blocked as shown. Thus, we may write:
[red,r = 2 0 0 2, which reduces to A I + B ~ :
[red,a = 1 1 1 I, which corresponds to A I .
4.11 Study Sections 4.1.4 and 4.4.
fred = 18 0 2 0 0;
by standard reduction, [red = A] +A ~ + 2E] + 2T] + 2h
4.12 Study Sections 4.1.4 and 4.5.
(a) C
3
0 C, = 53; the characters of C
3
are blocked below:
5
6
E C
3
S
6
exp u21l/3)
A
9
A
u
1
1
1
1
1
1
1
•
e
1
•
e
1
•
e
1
•
e
1
1
1
1
1
1
1
•
e
1
£;
•
£;
1
•
e
1
•
£;
£;
(b) D
2
0 C, = D
2h
; the characters for D ~ are blocked below
3u
E C (Z) C (y) C (x)
i cr(xy) cr(zx) cr(yz)
2h 2 2 2
A 1 1 1 1 1 1 1 1
9
B 1 1 1 1 1 1 1 1
19
B 1 1 1 1 1 1 1 1
2g
B 1 1 1 1 1 1 1 1
3g
A 1 1 1 1 1 1 1 1
1u
B 1 1 1 1 1 1 1 1
1u
B 1 1 1 1 1 1 1 1
2u
B 1 1 1 1 1 1 1 1
D
360 Tutorial Solutions
(a) E 2C
4
C
2
20'v 2CTd
f
3n
= 18 2 2 4 2= 4A
I
+A
2+2BI
+B
2+5E.
(b) E 2C
3
3C; O'b 2S
3
30'v
f
3n
= 12 0 2 4 2 2 =A ; + A ; + 3E' + 2A;' + E"
(c) E 2C
4
C
2
2C; 2C;' i 2S
4 O'b 20'v 20'd
f
3n
= 15 1 1 3 1 3 1 5 3 1
A
Ig
+ A
2g + BIg
+ B
2g
+ E
g
+ 2A
2u
+B
2u
+ 3E
u.
(d) E 8C
3
3C
2
6S
4
60'd
f
3n
= 27 0 1 1 5 = 2A
I
+ 2E + 2T
I
+5h
o 3 I
3C;
o
4.14 Study Sections 4.1.4 and 4.4.
The symmetry operations on the outofplane p orbitals of B have the following
effects: E leaves all orbitals unmoved; C
3
and S3 move all orbitals; C moves two
orbitals and inverts the third; O'b inverts all three orbitals; o, moves two orbitals and
leaves the third unchanged. Hence:
D
3h
I E
fred 3
By standard methods, fred = A ;' + E".
4.15 Study Section 4.3.
(a) 1(1)2+ 2(_1)2 + 2(1)2+ 1(_1)2 + 3(_1)2 + 3(1)2 = 12;
(h = 12, n = I; h/n = 12).
(b)f
Eg
: 1
2
+ i(i) + (_1)2 + i(i) + t2+i(i)+a+ t2+i(i)
=8' (h =8 n = l: h/n =8)
r Eg* evalua;es as r Eg', .
We may note that, in this particular example, had we added together first the two
parts of E
g
to give 2 0 2 0 2 0 2 0, then h/n would have been 4: but the
equation would have summed to 2(2)2 + 2(_2)2, or 16, which is quite erroneous (see
also Example 4.9).
(c) For i :F j the sum is zero.
SOLUTIONS 5
5.1 Study Sections 5.2 and 5.2.1.
H = [1i
2
/ (2Il )]( V
I
2
+ V/)  V(r)
where the subscripts refer to electrons 1 and 2 on the helium atom.
V(r) = Zeffe2 /(41t601"l)  Zeffe2 /(41t601"2) + e2/(41t601"d
where rl and r: are distances of electrons 1 and 2, respectively, from the nucleus and
r12 is the distance between the two electrons; then, the wave equation for He
becomes
+  4:: ( Zeff + Zeff  r
1
)W = EW
orr 12
1 2
Tutorial Solutions
where the effective charge Zeffis (from Slater's rules[2
1
) 1.70.
5.2 Study Section 5.2.2 and Appendix 7.
361
Ca)
J
OO In r
m
N
2
r
2
exp(2rla
o)
dr sinCe) de J_ d ~ =
o 0 0
1
The integrals are (aj2)3 [(3), 2 and 2n, so that N = (na ~ r
l
/
2
; 'V = (na ~ r
l
/
2
exp(
rlao).
(b) P = 4;la ~ exp(2rla
o)(lIpm).
(i) 2.6 x 10'5; (ii) 1.02 x 10'2.
5.3 Study Section 5.4.
(a) 8; (b) 0; (c) 12; (d) 24.
5.4 Study Section 5.2.
(a) C3v: 2pz spans AI and (2px, 2py) span E; Is and 2s each span AI. Nonzero
overlap can occur for N(2pz) and H(ls): AI C!9 AI = AI [SALC (lIV3)('VI + 'V2 + 'V3)],
and for N(2px, 2py) and two H(ls) that transform to give the SALCs (lIV6)(2'VI  'V2
 'V3) and (lIV2)('V2  'V3): (E C!9 E) C!9 AI = (AI +A
2
+ E) C!9 AI = AI +A
2
+ E. N(2s)
can give nonzero overlap with H(ls): AI C!9 AI = AI. For a bond angle less than 120°,
nonzero overlap is expected for s and p; If the angle equals 120° overlap will be
zero because the nodal plane of pz bisects the s orbital; this example shows an
integral vanishing even though the symmetry is correct for a nonzero result.
(b) In C
4v
))' spans B
2
, z spans AI and x
2
 l spans B]. Thus, B
2
C!9 AI C!9 BI = B
2
C!9
B
I
= B
2
, and the integral vanishes.
5.5 Study Sections 5.6 and 5.6.1, Figure 2.11 and the C
4v
character table.
Set up a table of ORd
n
(n = 15) for all operations in ~ v .
0 0 o 3 0 0
0a I
0 0
a'
E c C C
a
v
ad
4 4 2
v d
d d d d d d d d d
1 1 1 1 1 1 1 1 1
d d d d d d d d d
2 2 3 3 2 2 2 3 3
d d d d d d d d d
3 3 2 2 3 3 3 2 2
d d d d d d d d d
4 4 4 4 4 4 4 4 4
d d d d d d d d d
5 5 5 5 5 5 5 5 5
Using rule 2, we form the representation [red = 5 1 1 1 1 1 1 1 or concisely, 5
1 1 1 1, which is reducible toA] +B
I
+B
2
+E. The following algorithm enables
reduction to be programmed: it is set for C
4v
, but is modified easily for other point
groups.
Set up data: array1(5,5) contains the characters of C4v, stored by columns; array2(5) contains
the nwnber of operations in its symmetry classes; array3(5) contains the representation to be
reduced; swn(5) holds the the nwnbers of each symmetry class, in the order set by array1; r is
the nwnber of irreducible representations, 5 in this example.
362
Tutorial Solutions
reduced; sum(5) holds the the numbers of each symmetry class, in the order set by arrayl; r is
the number of irreducible representations, 5 in this example.
tor countl = 1 to r do
sum(countl) = 0.0
tor count2 = 1 to r do
sum(countl) = sum(countl) + arrayl(countl,count2)
x array2(count2) x array3(count2)
end count2
tor sum > 0 print sum(S)
end count2
end count 1
stop
We set up now the five projection operators Pu. = ~ R X: (R)OR for C
4v
. For c:=A
1
,
we have PAl d, = 8dj • Working through d:; to d, we find PAl d, = 0 (n = 25), so we
consider next PEl d., For PBI d
s,
we have PEl d, = I (d.) + (1)(d
s)
+ (1)(d
s)
+ 1(d)
+ I(d
s)
+ I(d,) + (l)(d
s)
+ (I)(d,) = 8d,. and PEld
n
= 0 (n = 14); similarly, P
E
d
z
= 4, and so on. The totality of results is tabulated below.
Orbital Irreducible representation P(a)d(n) Form,d
n
d Type
(a)
Dimension
(ri)
n
d A 1 8d
2
Z
1 2 1
d E 2 4d (zx,yz)
2 2
d E 2 4d (zx,yz)
3 3
d B 1 8d xy
4 2 4
d B 1 8d
2 2
X 
Y
S 1 S
5.6 Study Sections 5.6, 5.6.1 and 5.6.2.
Using again rule 2 for constructing symmetryadapted orbitals, we obtain first the
reducible representation below:
E 2C
4
C
z
2C; 2C;' i 28
4
crh 2cr
v
2crd
Ced = 4 0 o 2 0 0 o 4 2 0
which may be reduced to A
zu
+ B
zu
+ E
g
. We use now the projection operator Pa. with
the function pz over the irreducible representations A
zu
, Bi« and E
g
:
Tutorial Solutions
0
R
R E C C
3
C
C' C' C' ,
C' ,
i 5
53
O"b O"V O"v' O"d
0"'
4 4 2 2 2' 2 2'
4 4
d
P1
P
1
P
2
P
4
P
3P1P3
P
2
P
4
P P
2
P
4
P P
1
P
3
P
2
P
4 3 1
PaP1
Normalized
1
4(p + P )
(p
+ P + P
+ P )
+ P + P
2 1 2 3 4
1 2 3 4
1
P
4
)
4(p
+ P
 P )
(p  P
2
+ P 
 P
2
2 1 3
1 3 4
1
 P )
4(p  P )
vI2(P
1 3
1 3
363
We need a second function for the E
g
representation. The problem is simpler than
that which we encountered with the carbonate ion. In all point groups containing
C
4
, a second generating vector related to the first by C
4
provides a second
degenerate function. Thus,
0
R
R E C C
3
C C' C'
C' , C' ,
i
5
53
O"b O"V
0"'
O"d O"d'
4 4 2 2
2'
2
2'
4 4
v
P
2
P
2
P
3
P
1
P
4
P
4
P
2
P
1
P
3
P
4
P
3
P
1
P
2
P
4
P
2
P
1
P
3
so that PEgI>2 = 4(P2  P4) which, when normalized, is (1/"2) (P2 P4).
5.7 Study Sections 4.1.4 and 5.4.
(a) C
2h
: A
g
0A
g
=A
g
B
g
0 B
g
=A
g
Au 0A
u
=A
g
B; 0 B; =Ag
A
g
0 B
g
= B
g
B
g
0 Au = B
u
Au 0 B; = Bg
A
g
@Au=A
u
B
g
0 B; =A
u
A
g
0 B; = B;
(b)T
d
: AI 0A
1
=A]
A] 0A
2
=A
2
A]0E=E
A] 0 T
1
= T
1
AI 0 T
2
= T
2
5.8 Study Section 4.4.
(a) C
4v:A2
+ B] + E
(b) D
4
d: E
1
+ E
2
+ E
3
A
20A2=A1
A
20E=E
A
20
t, = T
2
A
20
T
2
= r,
E0E=A
1+A2+E
E0 T
1
= T] + T
2
E0T
2
= T] + T:
T
1
0 T
1
= Al + E + T] + T
2
T
1
0 T
2
=Az + E + T] + T2
T
2
0 T
z
= A] + E + T
1
+ T
2
364 Tutorial Solutions
5.9 Study Sections 5.6.2 and 5.6.3.
Using 'rule 1', we obtain the representation
E
o
o
By reduction, fred = 24" + 2E".
5.10 Study Sections 5.5, 5.6.1 and 5.6.2.
(a) Referring to the character table for Td, we see that the characters under E are 1
each, so that XE = 4. The C
3
operations leave one hydrogen atom unmoved, so that
x
C3
= 1. Both the C
2
and S4 operations move all hydrogen atoms, so that xC2 = xS4 =
O. The ad operation leaves two hydrogen atoms unmoved, so that xa d = 2. Hence,
2
E
4
which reduces to AI + T
2
• The character table shows that the (spherically symmetric)
hydrogen s orbitals span the totally symmetric AI, because they transform as r, or (x
2
+y2 + i)ll2.
(b) The p orbitals span T
2
, so that carbon sand p orbitals can bond with hydrogen s
orbitals under both bases through (AI + T
2
) SALCs.
(c) The d orbitals span E and T
2
in T
d
; hence, only the d
xy
, d
zx
and dxy, spanning T
2
,
can contribute to the bonding. The other d orbitals would give vanishing integrals
with A] and T
2
because of their different symmetries. We can display these results
more fully as folllows:
T
d
E 8C
3
3C
2
6S
4
6ad
AI, s I I I 1 I
hp 3
()
I I I
AI + T
2
4 I 0 0 2
Forf(A
I
+ T
2)sd't,wehaver
=4 0 0 2=A
I+T2
.
For f(A
I
+ T
2)p
dr, we have I' = 7 I I I 3 =A] + 2h
Each integral contains AI, and can be nonvanishing. However, for d.x2 _y2. we obtain
(AI + T2)dx2y2, which leads to the products (AI (8) E) + (T
2
(8) E) = E + T
1
+ T
2
that
vanish.
5.11 Study Sections 5.5, 4.1.5, 4.6 and 4.1.4.
transI,2Dichloroethene: C
2h
.
E C
2
Hydrogen Is: f. = 2 () 0
Chlorine 2p: f
p
= 6 0 0
5.12 Study Sections 3.3.4,5.6.1,5.6.2 and 2.4
ah
2 =A
g
+ B
g
2 = 2A
g
+Au+ B
g
+ 2B
u
Tutorial solutions 365
"
\
z , C
2
c    T        ~ y
5.13 Study Sections 4.1.3 and 5.6.3 and Figure S5.1.
Translational displacements
About z: E and C
2
leave a vector along z
unchanged, whereas i and O"b reverse it.
Hence, the characters are, in the order
E, C
2,
i, O"b, 1 1 1 1.
About x: E and O"b leave x unchanged;
C
2
and i reverse its direction. Hence, the
characters are 1 I 1 1.
About y: y behaves as does x.
x
 
in a cube containing the octahedral ion, then the twofold axes are [0 I I], [10 1 ] and
[I 10]. It is easy to confirm (see Section 2.5.1 or Section 8.4) that the angles
between [Ill] and each of the twofold axes are 90°, and between any pair of twofold
axes 120°. The species with cis ligands, as given, is optically active and may be
resolved into D and L forms.
Rotational displacements
About z: none of the symmetry operations changes the sign of R
z
, Figure S5.1.
Hence, the characters are in order, 1 1 1 1.
About x: E and i leave R; unchanged; C
2
and O"b change its direction. Hence, the
characters are I 1 1 I.
About y: y behaves as does x.
Product terms
The characters for product terms may be obtained by multiplication. Thus, for x
2
we
have e(_1)2 (_1)2 e, or I 1 1 1. For yz, we have 1
2
(1) x 1 (_1)2 I X (1), or 1 1
1 1. The assignments in character table ~ h are, thus, confirmed. (The
manipulations with degenerate irreducible representations can be a little more
involved).
SOLUTIONS 6
6.1 Study Section 6.2.1 and Appendix 8.
From the Is.Is graph:
(a) Sis,Is(H2l = 0.57;
(b) SIs,Is (H2) = 0.75;
(c) PIIIlIl< = 2.10 (graph); differentiating Sls,2p with respect to P and equating the
derivative to zero gives p
3
/3  1 = p; solve by successive approximations; Proax =
2.104.
6.2 Study Section 6.2.4.
Be is (1s)2(2si; B ~ is (1S<1
2
) (1S<1*)2 (2s<1
2)
(2S<1*)2 [or (1S<1g)2 (Is<1
u)2
(2SO"g)2
(2S<1
u)2];
overall antibonding; K = 0; Be does not exist as a stable species.
Cis (Isi(2s)\2p)2; C
2
is (1S<1g)2(1S<1
u)2(2s<1g)2(2s<1u)2
(2p7t.l; bonding; K = 2; C
2
is
more stable than its single atoms.
366
Tutorial solutions
6.3 Study Section 6.2.3 and Appendix 11.
Let the o bond be formed by the two pz orbitals. Then, for point group Deeh we
generate [a = 2 2 2 0 0 0, which reduces to L; + L: . With the px and py orbitals,
we generate I', = Il, + Il., The normalized orbitals are:
Bonding Antibonding
IJ': (1/v2)(p
+ P
z
2
)
IJ':
(1/,,12) (p
 P
Z
, 2
)
g Z,l , u Z,l
{
(1/,,12) (p
+ P
X
, 2
)
{
(1/,,12) (p
 P
x
2
)
X,l X,l
Tl : Tl :
,
u
( 1/v2)(p
+ P
y
, 2
)
g
( 1/v2)(p )
y,l y,l
 P
y
, 2
6.4 Study Section 6.3.1 and Appendix 11.
In D
6
, the representation becomes
2 o o o
E
6
I    
[red
which reduces to A
2
+ B
2
+ £1 + £2. We apply projection operators to a function 'VI
on carbon atom 1, as follows:
E C C
5
C C C C' C' C'
C' r
C' , C' ,
6 6 3 3 2 2a 2b 2c 2a 2b 2c
P
A
1/1
1
1/1
1
1/1
2
1/1
6
1/1
3
1/1
5
1/1
4
1/1
1
1/1
3
1/1
5
1/1
2
1/1
4
1/1
6
2
P
E
1/1
1
=
21/1 1/1
2
1/1
6
1/1 1/1 21/1
a a a a a a
1
354
1
These functions give the normalized orbitals:
A
2
: (l/...JG)('VI + 'V2 + 'V3 +'V4 +'V5 + 'V6)
£1 : (l/...J12)(2'V1 + 'V2  'V3  2'V4  'V5 + 'V6)
Continuing in this manner with other functions leads to the remaining SALCs in
(6.57).
6.5 Study Sections G.3.1 and 6.3.2.
From the general structure
He
2 ~ _ e H
H ef 2
2
Tutorial Solutions
we can write the Huckel determinant:
y 1 1 1
1
Y
0 0
=
0
1 0
Y
0
1 0 0 y
367
Expansion gives /  31 = 0, so that y = 0, 0, ±./3. The matrix is symmetric, and
Jacobi diagonalization gives the eigenenergies E and eigenvectors:
ex+ ex ex ex 
0.70711 0 0 0.70711
0.40825 0.74642 0.33094 0.40825
0.40825 0.08661 0.81189 0.40825
0.40825 0.65981 0.48095 0.40825
The first three orbitals are occupied. Thus, Pl2 =Pl3 =PI4 = 0.70711 x 0.40825 x 2
= .57735 = 1/./3. (Actually, O.70711 = 1/./2 and 0.40825 = 1/./6.). Hence, the total
bond order P = 3 + 3/./3 4.732. It follows that the free valence of C\ is zero and
that of the other three atoms is ./3  (1/./3), or 2/./3, each.
6.6 Study Sections 4.1.4, 5.6, 6.3.1, 6.3.2 and Appendix 11.
The point group of naphthalene is D
2h
and the general structure is
8 1
C C
7 ""c 2
I I I
6 C C C 3
5 4
We can use the outofplane PI orbital to form a representation:
o 2 0 0
cr(xy) cr(zx)
10 0 2
which reduces to 2B
2g
+ 3B
3g
+ 2
11
u
+ 3B
l u
. The three mutually perpendicular o
planes invoke all other symmetry elements in D
2h
. All atoms are inverted in the
molecular plane xy; thus, the irreducible representations must be antisymmetric for
the and only B
2g
, B
3g
, Au and BIll will suffice, as we have found
above. We consider atoms 1. 2 and 9 because they are related by symmetry to all
others, and obtain a table of OR\I/; values:
J1
2 h
E C (z ) C (y) C (x ) i
cr(zx) cr(yz)
222
1/1
1
1/1
1
1/1
5
1/1 1/1 1/1 1/1 1/1
4
1/1
8 8 4 5 1
1/1
2
1/1
2
1/1
6
1/1 1/1 1/1 1/1 1/1
3
l/J
7 7 3 6 2
l/J
9
l/J
9
l/Jl0
l/J
9
l/J
10
l/Jl0
l/J
9
l/Jl0
l/J
9
368 Tutorial Solutions
We apply the projection operator, Pa;'Va.,i = LR XR OR 'Va.,i, and list here those
functions that are not annihilated:
 )
8
 )
7
+ )
8
+ )
7
= + 
= + 
236
= 
= 
= (l/vZ) 
=  +
145
=  +
= (liZ)( + +
145
= + +
(l/vZ) + )
9 10
4>'
1
4>'
2
4>'
3
4>'
4
4>'
5
4>'
6
4>'
7
4>'
8
4>'
9
=
A:
u
B
lu
B :
3g
B :
2g
We could now set up a 10 x 10 blockfactored matrix as we did for benzene.
However, we know that each factor corresponds to an irreducible representation, so
that there will be 2 x 2 matrices for B
2g
and Au and 3 x 3 matrices for B
3g
and B
1u
.
Taking Bs«; for example, we obtain first the H,; terms:
H = J 4>' Jf 4>' dr
88 8 0 8
= (1I4)J + +
1 4 5
H = J 4>'Jf 4>' d'r
89 8 0 9 .
= (1I4)J + +
1 4 5
H = J 4>'Jf 4>' d'r
8,10 8 0 10
+ )Jf + + + ) d'r = (3.
8 0 2 3 6 7
= (l/ZvZ)J + + + )Jf + .1. ) dr = (3vZ
1 4 5 8 0 9 't'10 •
H = H = (3
98 89 .
H = J 4>'Jf 4>' d'r
99 9 0 9
= (1/4)J + + + 1/17)Jf
O
+ + + dr
= a + (3.
H =J4>'Jf4>' d r
9,10 9 0 10
= (1/ZvZ)J +
2 3
H = H =
10,8 8.10
H = H =
10,9 9.10
+ + )Jf
o
+ 1/110) dz = O.
(3VZ.
O.
H = J '/" Jf,/,' d'r
10,10 't'10 0't'10
= (1/Z)J + )Jf + d'r = a + (3.
9 10 0 9
Tutorial Solutions 369
which leads to:
a  e
(3 (3';2
Y
1 ';2
(3 a +
(3
 g
0 = 0, or 1 y + 1 0 = 0
(3';2
0 a + (3
 g
';2
0 y +
1
which factorizes further to give (y + I)(V +Y  3), so thaty = I, (I ± ..J13)/2. Thus,
E = ex. + ex. + ex.  1.3028. Taking v, = I, we have:
whence CS1 =0, C91 =0.81650, CW,1 =0.57735. Thus, the 1t molecular orbital for E
= ex. + is:
O.81650(1I2)(\jI2 + \jI3 + \jI6 + \jI7) +0.57735(1I..J2)(\jI9 + \jIw), or
E = ex. + ex.:l1>B\u = O.40825(\jI2 + \jI3 + \jI6 + \jI7) +0.40825(\jI9+ \jIw).
We proceed in this manner for all SALes; the results are summarized in order of
increasing energy:
s; B2g
B
3g
s.; Au
0.30055 0.26287 0.39959 0.00000 0.42533
0.23070 0.42533 0.17352 0.40825 0.26287
0.23070 0.42533 0.17352 0.40825 0.26287
0.30055 0.26287 0.39959 0.00000 0.42533
0.30055 0.26287 0.39959 0.00000 0.42533
0.23070 0.42533 0.17352 0.40825 0.26287
0.23070 0.42533 0.17352 0.40825 0.26287
0.30055 0.26287 0.39959 0.00000 0.42533
0.46140 0.00000 0.34705 0.40825 0.00000
0.46140 0.00000 0.34705 0.40825 0.00000
0.6180313 1.000013 1.302813 1.618013
B
2g
B3g e: Au B
3g
0.42533 0.00000 0.39959 0.26287 0.30055
0.26287 0.40825 0.17352 0.42533 0.23070
0.26287 0.40825 0.17352 0.42533 0.23070
0.42533 0.00000 0.39959 0.26287 0.30055
0.42533 0.00000 0.39959 0.26287 0.30055
0.26287 0.40825 0.17352 0.42533 0.23070
0.26287 0.40825 0.17352 0.42533 0.23070
0.42533 0.00000 0.39959 0.26287 0.30055
0.00000 0.40825 0.34705 0.00000 0.46140
0.00000 0.40825 0.34705 0.00000 0.46140
370 Tutorial solutions
The bond orders and free valences can now be calculated; it should be evident that
the formal charges are unity on each atom.
Pll == 2(0.30055 x 0.23070) + 2(0.26287 x 0.42533) + 2(0.39959 x 0.17352) +
2(0 x 0.40825) + 2(0.42533 x 0.26287) == 0.725.
The complete results follow:
P12 == P34 == PS6 == P78 == 0.725; P23 == P67 == 0.603; P9,IO == 0.518;
P4,lO == PS,IO == P89 == P9l == 0.555.
F
l
== 1.732  P12  P19 == 0.452 == F
4
== F
s
== F
8
;
F
2
== F
3
== F
6
== F
7
== 0.404;
F
9
== FlO == 0.104.
E" (the sum of the energies over the occupied Mas) ==
D" (E" less 5 equivalents ofethene) ==
7t Configuration: (lbluiOb2gi(lb3i(2blu)2(laut
Lowest energy transition: Au (HOMO) B
2g
(LUMO), £. ==
6.7 Study Section 6.3.4.
Point group C
2v.
A representation on the basis of the pzorbitals gives:
erIC
1
__.....:::.o,_..::..L_=::...Jl..._
Ced I 5
We apply the operator ORto 'Vl (on N), 'V2 and 'V3 (on C
2
and C
3;
the others are
linked by symmetry) and q/, (oxygen):
C
2v
E C
2
er
v
er v
Now, we apply the projection operator:
PA 1/1
1
= 0;
2
P
B
1/1
1
= 1/1
1
1
 .1. ).
'f'4 '
+ 1/1 I .
4
Thus, the SALCs are:
{
tJ>'
1
B:
tJ>'
1 2
tJ>'
3
A,' {
tJ>'
4
tJ>'
5
=
=
=
=
1/1
1
( lIv'Z)(1/1
2
(lIv'Z) (1/1
3
( lIv'Z)(1/1
2
(l/v'Z) (1/1
3
In constructing the Huckel matrix we use h
N
== 1.5 and k
C

N
== 1.0
H
ll
=a + 1.5; H
I 2
=fi...J2;
H
22
=a;
Tutorial solutions
H
13
= 0;
H23
H
33
= a
H
I 4
=0;
H
24
=0;
H
34
= 0;
H
44
371
H
I 5=0;
H
25
= 0;
H
35
= 0;
H
45
H
55
Hence the Huckel (blockfactored) matrix becomes
a. + 1.5  E (3.,12 a a a
(3.,12 a. (3 a a
o. =
a (3 a. + (3 a a
a a a a. (3
a a a (3 a.  (3
Making the usual substitution of y = (a  we obtain:
y + 1. 5 >/2 a a a
.,12 y 1 a a
o. =
a 1 y + 1 a a
a a a y 1
a a a 1 y  1
B
2
: 3rd order determinant solves to l + 2.51  1.5y  3.5 = 0, whence y = 2.5498,
1.1469 and 1.1963 (program POLY) so that E = a + a + and a 
AI: The 2nd order determinant solves to 1 y  I = 0, whence y = 1.6180 and
0.6180 so that E = + and a  We now obtain the true molecular
orbitals, proceeding as in earlier, similar problems.
Bonding orbitals (2B
I
+A
2
) :
<1>1 =0.7494'1'1 +0.3934('1'2+'1'5) + 0.2538('1'3+ '1'4);
<1>2 = 0.5029'1'1  0.0888('1'2+ '1'5)  0.6047('1'3 + '1'4);
<1>3 = 0.6015('1'2 '1'5) + 0.3717('1'3  '1'4);
Antibonding orbitals (B
I
+A
2
) :
<1>4 = 0.4307'1'1  0.5808('1'2 + '1'5) +0.2664('1'3+'1'4);
<1>5 = 0.3717('1'2 '1'5)  0.6015('1'3  '1'4);
E,. = 2(2.550 + 1.147 + = Pyrrole is formally equivalent to two C=C
bonds and one N contributing two electrons, that is, 2(a + + 2(a +
Hence, D." =
6.8 Study Section 6.4.1.
On model I, the orbitals are Px and and the hybrid h", so that the total density is p :
+ h,,2. With model 2, the orbitals are the linear combinations (l/...J2)(Px + h") and
372 Tutorial solutions
(1I...J2)(Px  h"), so that the total density is [(1I2)(P; + 2pxh" + h,,2) + (1I2)(P; 
2p,)z" +h,,2)), which evaluates to p; +h,,2.
6.9 Study Sections 5.6.2 and 6.3.3.
A ; : (\III + \112 + \113)/...J3 is spanned by s orbitals;
(2t/J 't/J  t/J )1';6 }
E' : 1 2 3 are spanned by pxand py .
(t/J2  t/J3)/';2
Thus, in matrix notation:
[
1/';3
2/';6
o
1/';3
1/';6
1/';2
The inversion of this matrix is its transpose, as it is orthogonal. Hence:
[
1/';3
1/';3
1/';3
2/';6
1/';6
1/';6
so that
\111 = (1I...J3)s + (2/...J6)px,
\112 = (1I...J3)s  (1I...J6)px + (1I...J2)py,
\113 = (1/...J3)s  (1I...J6)px  (1I...J2)py,
6.10 Study Section 6.7.2.
[PtC1
6
t , Ot, distorts to D
4h
. The axial PtCl bonds do not couple with the equatorial
bonds under D
4h
; hence, [CI = I'ax + [eq.
D
4h
E 2C
4
C
2
2C; 2 C ~ i 25
4 O"h
20"y 20"d
[ax 2 2 2 2 2 2 2 2 2 2
r, 4 0 0 2 0 0 0 4 2 0
By standard procedures, [ax =2A
2u
; [eq =A
l g
+ Big + E;
6.11 Study Section 6.3.1 and Figure S6.1.
~ v
(2)CH
Hc/ ""yH
r =
3 1 1
3
=
A
+ 2B .
2 (1) (3 2
1l
2 1
Proceeding as before:
A: ep'
=
(1/';2) (t/J  t/J ).
2 1
1
3 •
{
ep'
=
(1/';2) (t/Jl
+ t/J ).
2
3 •
B:
ep' t/J . 2
=
3 2
Tutorial solutions
The Hiickel determinant can be now constructed.
373
y 0
o y
o 12
E
o
2
Y
::;; 0,
2(3 2b
1
B: ex  f3'/2
1
(3
la
0
2
A: ex
2
(3 lb
1 l' i B: ex + f3'/2
1
2(3
Fig. 86.1 Molecularorbital energylevel diagram for the allyl cation.
where y =(a  E ) / ~ . Solving: y =0, ±'.J2, and E =a, a • ~ ' I ' 2 . The coefficients and
1t molecular orbitals are readily found:
j 1
2
3
1
112
11'1'2
112
2
11'1'2
o
11'1'2
3
112
11'1'2
112
<1>1 = (1I2)\j'I + (1I'I'2)'V2 + (1I2)\jI3
<1>2 = (1/'I'2)(\jI1  'V3)
<1>3 = (1/2)\jIl  (1I'I'2)\jI2 + (1I2)\jI3
B
I
(bonding)
A
2
(nonbonding)
B
1
(antibonding)
We may note that the allyl cation, radical and anion have the same molecular
orbitals under this approximation, but the number of electrons for A
2
symmetry
increases from 0 to 2.
6.12 Study Section 6.3.1 and Figure S6.2.
The Hiickel determinant in Solution 6.11 is now modified to
y + 1 1/2
12 y
o
o
o o
= 0,
374 Tutorial Solutions
c
where y is, as usual, (0.£)/13. Thus, we obtain £ = a  ~ for the B] representation,
and E = a ± ~ for A
2
; the correlation diagram is shown in Figure S6.2.
E
2f3
f3'/2

~ . ] f3

0 0
f3
f3'/2

2/3

2f3
0
f3
12
~
/3
13
OPEN THREE CLOSED THREE
CENTRE BONDING CENTRE BONDING
Fig 86.2 Correlation diagram between open and closed threecentre bonding in the allyl
cation.
In the closed case, the bonding electrons occupy the energy level a + 2 ~ : it is more
stable than the open case, which is to be expected since the 7t bonding has increased.
According to the extent of the interaction between C
1
and C
3
, so the energy levels
will be represented somewhere along the lines correlating the extreme conditions.
The symmetry of the system has increased nominally to that of D
3h
, for which we
have found previously the representation A" + E", wherein the two energies of a  ~
are degenerate.
6.13 Study Section 6.7.2.
Consider four atype orbitals directed along the Cu ~ N bonds. By the usual
procedures.we find Fj e a 0 0 2 0 0 0 42 O=A
1g+B]g+Eu;r,,=4
002
o 0 0 4 2 0 = A
2u
+ B
2u
+ E
g
. aBonding may take place through copper 4s,
3d; ; and 3d,2, forming d
2
sp3 hybrid orbitals.
6.14 Study Section Section 6.7.4.
Using ball and spoke equipment, we set up the following model:
A
B
F /
E/
D
Now consider the movement of point A under the operations of Oh:
Tutorial Solutions
375
o,
Movements of A Multiply by the characters of T
lu
E A 3A
8C 2B + 2C + 2£ + 2F 0
3
6C 2A + B + C + £ + F 2A + B + C + £ + F
4
3C A + 2D A  2D
2
6C' B + C + 2D + £ + F B  C  2D  £  F
2
i
D 3D
88 2A + B + C + £ + F 0
6
68 B + C + 2D + £ + F B  C  2D  £  F
4
3a"
2A + D 2A + D
6ad 2A + B + C + £ + F 2A + B + C + £ + F
Form the sum of the multiplied characters: 8A  80, which is normalized to (1/"';2)
(A  0). Similarly, the other two functions are (1/"';2)(E  B) and (1/"';2)(C  F).
6.15 Study Section 6.7.1.
(a) (i) I] = 1 1
2
= 2: L = 3, 2, 1 (F, 0, P);
(ii) I] = 2,1
2
= 3: L = 5,4,3,2, 1 (H, G, F, 0, P);
(iii) J
I
= 2, J
2
= 2: L' = 4,3,2, 1,0:
L' = 4, J
3
= 2: L = 6, 5, 4, 3, 2 (I, H, G, F, 0);
L' = 3, J
3
= 2: L = 5, 4, 3, 2, 1 (H, G, F, 0, P);
L' = 2,1
3
= 2: L = 4, 3, 2, 1,0 (G, F, 0, P, S);
L' = 1, J
3
= 2: L = 3, 2, 1 (F, D, P);
L' = 0, J
3
= 2: L = 2 (0).
(b) (iv) 1= 2, s = Ih; L = 2, S= Ih:
5 3 2 20
J = ,: OS/2, 3/2·
2 2
(v) h = 1, J
2
= 1: L = 2, 1, 0; SI = S2 = Y2: S = 0, 1;
L = 2, S= 0: J= 2 (1
0 2
);
L= I,S=O:J= 1 eP
I
) ;
L = 0, S= 0: J= 0 eSo);
L = 2, S= 1: J= 3,2,1 e03, 30 2, 30
d
;
L = 1, S = 1: J = 2, 1,0 ep
2
, 3p
l
, 3PO};
L = 0, S = 0: J = 0 eSo).
6.16 Study Section 6.7.1
(a) [Core](3p)s: L = J= 1, S = s = Y2: J =3/2, Y2 ep
3
/2, 2p1/2).
Another way of looking at (3p)s is (3p)6(3pr
l
, where we have a one pelectron
'hole'.
(b) [Core] (3S)I: L =I =0, S = 1/2: J = 1;2 eSI/2).
(c) [Core] (3s)o(3p)l: an excited state; L = J= 1, S = 1;2: J = 3/2, 1;2 ep3/2 , 2p]/2).
376 Tutorial Solutions
6.17 Study Sections 6.7.3 and 6.7.4.
n in d" Weak field
Configuration Unpaired e
1 (t)' I
2 (t)2 2
3 (t)3 3
4 (t)\e)1 4
5 (t)3(e)2 5
6 (t)4(e)2 4
7 (t)5(ei 3
8 (t)6(e)2 2
9 (t)6(e)3 I
10 (t)6(e)4 0
Strong field
Configuration Unpaired e
~ ) l I
(t)2 2
(t)3 3
(t)4 2
(t)5 I
(t)6 0
(t)6(e)1 I
(t)6(e)2 2
(t)6(e)3 I
(t)\e)4 0
6.18 Study Section 6.7.4.
From the Orgel diagram, the probable transitions are:
 1
v/cm
8700
14500
25300
3 A (F) 7 3r (F)
29 29
3A (F) 7 "t (F)
29 19
3A (F) 7 3r ( F )
29 19
Transitions "g' ~ 'g' are parity forbidden, but breakdown of this rule permits d ~ d
transitions of relatively weak intensity.
6.19 Study Section 6.7.1 and Table 6.9, and recall Hund's rule.
Electrons tend to occupy orbitals singly as far as possible, so that the state of highest
multiplicity corresponds with that of minimum energy. Hence:
4
5D
Where two states of the same multiplicity occur, as with d
2
and d
8
, that with the
higher value of L is the lower in energy. Thus, 3F is preferred as the ground term for
d
2
and dB.
6.20 Study Section 6.7.1.
We evaluate the number of combinations of two electrons of spin ±Y2, or ex, and ~ ,
among five d orbitals. It may be done by arranging electrons in boxes, of which the
following examples are given; we use M
L
= ~ m, and M
s
=~ s:
Tutorial Solutions
377
m
1
:; 2 1 0 1 2 11 11
L 5
I
a (3 1 way for: ±4 0
I
a a 4 ways for: ±3 1
I
a (3 5 ways for: ±2 0
I
(3 (3 8 ways for: ±1 1
I
(3 a 9 ways for: 0 0
There are, thus, 45 arrangements for the M
L
values. Since M
L
= 4 occurs once, a to
term is present. We subtract I from the remaining M
L
values:
M
L
±3 ±2 ±l 0
Ways 3 4 7 8
It is now evident that a 3F term exists. Subtract 3 from the remaining M
L
values:
M
L
±2 ±l 0
Ways I 4 5
We see now that a 'n term is present, and we subtract I from the remaining ML
values:
M
L
±I 0
Ways 3 4
Thus, there is a 3p term present, and subtracting 3 leads to
M
L
0
Ways I
which corresponds to I S. Thus, the set of terms for d
2
(d
8
) is:
10, 3F, ID, 3p, 1S, as in Table 6.9; 3F is the ground state term.
6.21 Study Section 6.7.4ff.
In tetrahedral symmetry, the axes of the d:
2
and d
x2

y2
orbitals lie midway between
the ligand positions, so that the e
g
energy levels lie below the h
g
levels; Zn
2
+ is d'";
no unpaired electrons; diamagnetic.
6.22 Study Section 6.7.4.
X= KiD = 6.53 x 10
7
m
3
kg" == 1.84 x 10
7
m
3
mol". NAlloll ~ /(3k
B
1) = 5.271 x
10
9
m
3
mol". Hence, 1.84 x 10
7
111
3
mol" = 5.271 x 10
9
m
3
mol" x 4S(S + I),
whence S(S+ 1) = 8.727, and S = 4.992, namely, 5 unpaired electrons; m._o = [5(5 +
2)]112 J.l.B = 5.92 llB.
6.23 Study Section 6.7.4.
Rotation of 90
0
about z interconverts d
y
: and dzx. (a) d
y
: and d
zx
remain degenerate.
(b) The degeneracies of d
y
: and d
zx
are split under the action of an applied field. (c)
378 Tutorial Solutions
Rotation about x interconverts d
xy
and dzx, (d) Rotation about y interconverts dxyand
d
yz
.
6.24 Study reference 56, or similar.
T
v
2
= 5 m
2 3 1
(8
2
= kg m 8 A
m )
kg
2
A
1
8
(6.105): B
(6.111): N
3
m
flo
flo
H
1
m
kg
2
A
2
= m 8
fl
o
H
= kg 5
2
A
1
l/(k T)
B B
J T
2
= J y2 8
2
m
4
= C y1 8
2
m
4
= ~ ~ ~ l ~ ~ ~ ~ A ~
H
2
(kg
2 2
A
2
) (kg
1
m
2
52 A
2
)
1
Nfl fl / (k T)
=
m 8 =
o B B
6.25 Study Section 6.3.1 and Appendix 11.
We now obtain the representation
D
6
E 2C
6
2C
J
C
2 3 C ~
3C ~ '
Cod
6
()
0
()
0 2
which reduces to ,12 + B
1
+ £1 + £2. We need to interchange the B
I
and B
2Iabeis
of
the D
2
character table when the C; and C;' axes are interchanged on the molecule.
6.26 Study Sections 6.3.16.3.3.
(a) C
2v
I
E C
2
cry cry
fred 5 3 3 5
=
A
2
+AB
I
(b) The solution via SALCs follows the standard procedure.
<PI = O.2610\jfj +O.5574\jf2 + O.4647\jf3 + O.4352\jf4 + 0.4647\jf5;
<P2 = O.65721f1 +0.43521j/2  O.18451f3  0.55741f4  O.1845\jf5;
<P3 =  O.7071\jf3 + O.7071\jf5;
<P4 =0 O.6572\jf[  0.43521f2  O.1845\jf3 + O.5574\jf4  O.1845IV5;
<P5 =0 O.261O\jf1  0.5574\jf2 + 0.4647\jf3 0.4352\jf4+ O.4647\jf5'
Tutorial Solutions 379
The order of the coefficients in any ~ i may vary according to the atom that is
numbered 2; the results here correspond to the diagram given in Section 6.3.3.
(c) £,. = 5a. + 5 . 5 9 6 ~ .
•
4>4'
a' ,
,/
,
.,
•
,/
....
•
1l ./ ,
1l
./
,
a"
<,
•
/' /' a"
<,
IP
3
, a
'
<,
l' 1
,/
,,/
, ,/
"'"
.,'
a'l
<,
,/
4>2'
<,
1l
"
<, 1l
l' 1
""
<,
1'1
a'
<,
./ a'
<,
.,
<, /'
<, ,/
" l' lIP
,/
1 '
a '
(a)
•
4>4'
a"
,/ <,
/' <,
•
•
,/ <,
1l ,/
<, 1l
l'
,/
" l'
a"
<,
•
,/
a"
<,
IP
3
, a '
"" <, ,/
'<
....... "
""
l' 1</> ~ "
,/ <,
1l
2' <,
1l
l' a
'
./
<,
l' <,
/'
a
' ,/
<,
,/
<,
,.
<,
l' 1 IP
./ ....
1 '
a'
ETHENE
CYCLOBUTANE ETHENE
(b)
Fig. 56.3 Molecularorbital energylevel diagram for the cycleaddition of two molecules of
ethene to form cyclobutane: (a) thermal, symmetryforbidden; (b) photochemical, symmetry
allowed.
6.27 Study Section 6.6 and Figures S6.3a,b.
Huckel theory applied to ethene gives the energy states (a,)2 or (n)2 (HOMO), and
(a,,)2 or (n*)2 (LUMO). Only HOMOHOMO and LUMOLUMO interactions are
symmetryallowed. Thus, we obtain the occupied bonding and antibonding
molecular orbitals for cyclobutane (a,)2 and (a,*)2 , Figure S6.3a. As there is no
decrease in energy compared to two molecules of ethene, the thermal process does
not take place. If ethene is excited photochemically to (n)l (n*)1 , bonding takes
place to give the molecular configuration (a')2 (a,,)2with a reduction in total energy,
so that the photochemical cycloaddition is symmetryallowed, Figure S6.3b.
380 Tutorial Solutions
SOLUTIONS 7
7.1 Study Section 7.1.
(a) 1, (b) 4, (c) 3, (d) 6, (e) 18, (066.
7.2 Study Sections 7.2.1,7.3 and 7.5.
Linear MX
z
: point group D
roh
:
:.B'
ooh
r
3n
E
9
2Crp
00
3 + 6cos(rp)
000",.
3 3 1 + 2cos(rp)
ooC
2
1
f
3n
= l:; + I1
g
+ 2l:: + 2I1
u
: subtracting the translational and rotational (R; and R;
only) contributions, [vib = l:; + l:;' + I1
g
. From direct products, l:;' and I1
u
infrared active, and l:; is Raman active (polarized).
Bent MX
z
: point group c.,
r.,
E
9 1
cr'
v
3
f
3n
= 3A
I
+ A
2
+ 2B
I
+ 3B
z
: subtracting the translational and rotational
contributions, f
Vib
= 24
1
+ B
z
. From direct products, AI and B
z
are active in both
infrared and Raman.
7.3 Study Seection 7.3.
D
6h
is centrosymmetric; therefore, no one mode can be both infrared and Raman
active. From the character table:
J¢A fJ. i ¢A d'r
=
a
(i
=
x, y, z)
19 19
J¢A uij¢A d'r
:1= a (ij
2 2
z2)
=
x, y,
19 19
Hence, A l g is Raman active (infrared forbidden) for i =j =z.
7.4 Study Sections 7.2.1 and 7.3, and Figure 7.2.
From the analysis in Section 7.2.1, Cib = A " + A ; + 2E'. From direct products, A ;'
and E are infrared active, and A; and E' are Raman active, polarized and
depolarized, respectively. The stretches normally have the higher frequencies, with
the symmetric lower than the asymmetric. Outofplane bends are generally of
higher frequency than inplane bends. Thus, we assign as follows:
01
U3
Symmetric BF stretch
Asymmetric BF stretches
Tutorial Solutions 381
692 em"
480 cm' U4
Outofplane bend
Inplane bends
7.5 Study Sections 7.2.1,7.3 and 7.4.
Point group C
3v
; use internal coordinates rl (P=O), r2 (PCl) and angles Ct. Then:
~ v
E 2C 3a
v
3
r 1 1 1 = A
r 1
1
r 3 a 1 = A + E
r 1
2
r 6 a 2 = (2)A + 2E
ex 1
We expect one x, in C. to be spurious (confirm through f
vib
) . In the usual way, we
find f
3n
= 4A) + A
2
+ 5E: ftr,rot =Al + A
2
+ 2E, so that f
vib
= 3A) + 3E; thus, C. =
AI + 2E. We use now direct products as follows.
Infrared: A [ A }
1 ® 1 ® A (E)
E 1
which leads to
AI @A
I
@A
I
(E) =.1
1
(E)
Al @E @A
I
(E)=£(A
1
+A
2+E)
which shows that both AI and E modes are infrared active.
Raman: A ® [ A
1
} ® A (E)
1 E 1
so that AI and E are also Raman active (AI polarized).
bend
PCl symmetric str;
P===O str;
+ ir;
+ ir;
+ ir;
7.6 Study Section 7.3 and 7.4
As before, the stretches correspond to the higher frequencies, with the P=O stretch
the highest of the three and the PCl symmetric stretch the lower of the remaining
two. Of the bends, the 267 em" vibration is symmetrical because it belongs to AI.
Thus, we obtain:
1291 cm
1
A' Raman polz.
1 '
487 cm
1
A' Raman polz.
i '
581 cm
1
E; Raman depolz. + ir; PCl asymmetric strs;
267 cm
 1 A R 1
. aman po z.
1 '
339 c m ~ : } E' Raman depolz. + ir; bends
193 em '
In all, 9 bands (3n  6), with complete coincidence between the infrared and Raman
spectra.
382 Tutorial Solutions
7.7 Study Sections 7.2.1 and 7.3.
We set up orthogonal axes at each atom (see Figure 6.37 with an additional set of
axes centred on the central atom M) of the [CoC1
6
f ion, point group We find as
follows:
21 0 3 3 1 3 0 5 3 3
which reduces to A
l g
+ E
g
+ T
l g
+ T
2g
+ 3T
l u
+ T
2u
. Subtracting the contributions for
translation and rotation (T
l g
+ T
l u
) leads to f
vib
= A
i g
+ E
g
+ T
2g
+ 2T
l u
+ T
2u
(15
vibrational modes in all). Using direct products, we find as follows.
Infrared: A
l g
® T
l u
® A
l g
(E
g
, T
2g
, T
l u
, T
2u
) ; infrared active in T.; only.
Raman:
A ® l ® A (E,
19 9 19 9
T
2g
T , T , T );
2g 1u 2u
Raman active in A
i g
(polarized) and 7'2g.
For the complex in D
4h
symmetry:
D
4h
E 2C
4
C
2
2S
4 ah 2a
v
2ad
f
3n
21 3 3 3 1 3 1 5 5 3
which reduces to 24
1g
+ A
2g
+ Big + B
2g
+ 2E
g
+ 3A
2u
+ B
2u
+ 4E
u
. Subtracting the
translational and rotational contributions leads to f
Vib
= 2A
l g
+ BIg + B
2g
+ E
g
+ 2A
2u
+ B
2u
+ 3E
u
• Then
Infrared: A
®
[ ;2U] ® A (B
B E, A B E );
19
,
2g' 2u' 2u' 19 19
9 u
u
infrared active
in A
2u
and E:
A
Raman:
19
B
A ®
19
® A (B ,
B E,
B
A B
E J:
19
19 19 2g'
9
2u' 2u'
u
2g
E
Raman
9
active in Al g (polarized), Big, B
2g
and E
g
. Thus, the two forms of the complex may,
in principle, be resolved by their infrared and Raman spectra.
Tutorial Solutions 383
7.8 Study S ctions 7.2.1 and 7.3.
D
6h
E 2C
6
2C
3
C
2
3C; 3C ;' i 2S
3
2S
6 crb 3crd 3cr
v
VA 12 0 0
()
4 0 0 0 0 12 0 4
r., 36 0 0 0 4 0 0 0 0 12 0 4
f
3n
= 24
1g
+ 24
2g
+ 2B
2g
+ 2E
1g
+ 4E
2g
+ 24
2u
+ 2B
l u
+ 2B
2u
+ 4E
1u
+ 2E
2u
.
Subtracting the translational and rotational contributions (..1
2u
+ E
1u
+ ..1
2g
+ EI,J
gives f
Vib
= 24
1g
+ A
2g
+ 2B
2g
+ E
1g
+ 4E
2g
+A
2u
+ 2B
l u
+ 2B
2u
+ 3E
l u
+ 2E
2u
. From
direct products. in the usual way, we find as follows:
Infrared active: ..1
2u
, 3E
1u
. Raman active: 24
1g
(polarized), E
1g
, 4E
2g
•
Chlorobenzene belongs to point group e
2v
; from a cyclic interchange of axes, the
molecular plane becomes cry:
E
12
36
4
4
12
12
cry
4
4
Now, f
3n
= 124
1
+ 4..1
2
+ 12B
1
+ 8B
2
, and f
Vib
= lIA
I
+ 3..1
2
+ lOBI + 6B
2
. From
direct products, we find that the infrared active modes are AI, B
1
and B
2
, and the
Raman active modes are AI, A
2
, B
1
and B
2
. Summarizing:
C H
6 6
Infrared A ,3E
2u 1u
C H NO
652
llA , lOB, 6B
1 1 2
Raman 2A ,E ,4E 11A, lOB , 6B (coincident with
1 9 19 2g 1 1 2
the infrared) , plus 3A
2
The mutual exclusion rule applies to benzene because it is centrosymmetric.
7.9 Study Appendix 11 (correlation table for D
6h
) .
The vibrational modes under f
Vib
(sec Solution 7.8) correlate as:
V b V b V b
6h 2v 6h 2v 6h 2v
2A ~ 2A E ~ A + B 2B ~ 2A
19 1 19 2 2 1u 1
A ~ B 4E ~ 4A + 4B 2B ~ 2B
2g 1 2g 1 1 2u 1
2B ~ 2B A ~ B 3E ~ 3A + 3B
2g 2 2u 2 1u 1 1
2E ~ 2A + 2B
2u 2 2
Hence, the active modes in chlorobenzene are as follows:
Infrared: 1IAI, lOBI and 6B
2
.
Raman: 1L4
1
, lOBI and 6B
2
(coincident with the infrared) plus 3A2.
384 Tutorial Solutions
These results may be confirmed through r 3n and direct products on chlorobenzene
itself, and are in complete agreement with those found in Solution 7.8.
7.10 Study Sections 7.2.1,7.3 and 7.4.
PCls belongs to point group D
3h,
and the following vibrational data are available (see
Section 7.4).
Stretches: 2A ; , A; and E';
Bends: A , 2E' and E".
(a) PCl
4Br
with the Br equatorial belongs to point group CZy. From the correlation
table for D
3h
(see Appendix II), we have:
D
3h
CZy D
3h
CZy
A; AlE' AI + B
z
E" A
2
+ B
I
Stretches: 3A
1
+ B
1
+ B
z
Bends: 2AI +A
z
+ 2B
I
+ 2B
z
(b) PCI
4Br
with the Br axial belongs to point group C3y. From the correlation table
for D
3h
(see Appendix II), we have:
D
3h
C3y D
3h
C3y
A; E'
Stretches: 3AJ + E
Bends: Al + 3E
The results in (a) and (b) may be confirmed, if desired, by obtaining r
3n
and then
forming the appropriate direct products in each case.
7.11 Study Section 7.6.
The ground state of methane is I AI and the given excited states are:
(a) (la1)2 (ltz)s (2al)l: AI 13) 1
2
13) A I = 1'z. Spins are Y2 each, so that S = 0, 1. Spin
states are IT
z
and 3
Tz.
(b) (Iad
z
(ltz/ (2tz)1 : A
1
® T: ® T: =A] + E + 1'1 + Ti. Spins are Y2 each, so that S
= 0, I. Spin states are l
AI,
3
A1,
IE, 3E, ITj, 3
TI,
IT
z,
3T
2.
Only I
A1
IT
z
is fully
allowed. A second 1AI IT
z
transition is spinallowed for 2al 2iz.
7.12 Study Section 7.6.
The ground state of buta I ,3diene, point group C
Zh,
is (lau)z (lbi (2a
u)0
(2bg)°.
Possible transitions are lb, 2a", lb, 2b
g
, l a., 2a
ll,
la, 2b
g
, and the excited
states are (lall)z (lbg)1 (2a
ll
) 1 (2bJ' , (la,i (Ib
J
I (2a,l (2bg)l, (lau)1 (lbg)z (2a
u)1
(2bg)° and (lau)1 (lbi (2a,,)0 (2b,/. Their symmetries are given by the direct
products zl, 13) B
g
13) Au =B
lI
, A
g
® B
g
13) B
g
=A
g
, Au 13) A
g
13) Au =A
g
, All 13) A
g
13) B
g
=
Bu. The character table for C
2h
shows that the dipole moment components x, y and z
span Au and B; Thus, we form the direct products
Tutorial Solutions 385
A
g
® Au ® A
g
(B
u
) = Au(Bg)
A
g
® B; ®A
g
(Btl) = B; (Ag)
Thus, there are two 7t 7t* transitions I A
g
'a, corresponding to Ib, 2a
u
and
la, 2b
g
.
7.13 Study Section 7.4.2.
The HCN molecule belongs to point group em. We generate
c., E ... OOO"v
3
9
3
3 +
3
3 = E+ + 3n.
Rotational and translational components span I+ and 2n, so that r
vib
= 2I+ + n.
For infrared activity, we form the direct products
L' @ [ • 2L', IT > 2L', IT, 2IT, L' + L + IT.
For Raman activity:
+ +
, IT, ZIT, + + IT, Z!J. , IT + .
Thus, 2L+ and n are active in both the infrared and Raman; n is doubly degenerate
and corresponds to the bend modes:
v (HC)/cm
1
v (CN)/cm
1
v (bends)/cm
1
123
3311, Z097, 71Z, IT
The absence of a centre of symmetry permits the infrared and Raman bands to
coincide.
7.14 Study Sections 7.3. L 7.3.2 and 7.4.2.
The symmetry of the ion is C
2v
or C, if bent, but C",v or D"'h if linear. (a) The ion is
linear, because a bent triatomic species would produce 2 vibrations in both infrared
and Raman spectra. The structures are FHF and FDF, because HFF and
DFF(C",v) would give 3 infrared and Raman bands (see Problem 7.13) From a
comparison with the analysis of CO
2
(see Section 7.4.2), the infrared activity is
I: and Il., and the Raman activity I; . (b) The vibration modes are:
0 v Symmetric stretch
1
v Asymmetric stretch
2
o o o
v Two (degenerate) bends (inplane
3
and outofplane of diagram)
386 Tutorial solutions
The data show that U I does not change on replacing H by D, so that it will be the
fully symmetric Ramanactive L; .The asymmetric stretch U z will be the infrared
active L:, and the bend modes U 3are infraredactive flu.
7.15 Study Sections 6.7.3, 7.6.1 and 7.6.2.
We deduced (see Section 6.7.3) that (elg)z ~ IA
Ig
+ 3A
zg
+ IE
zg.
Similarly, (ezu)z ~
IA
Ig
+ 3A
zg
+ IE
zg.
Hence, (elg)z (ezu)z ~ eA
Ig
+ 3A
zg
+ IEzg) ® eA
Ig
+ 3A
zg
+ IEzg)
~ IA
Ig
+ 3A
zg
+ IE
zg
+ 3A
zg
+ lA
lg
+ 3A
Ig
+ 5A
Ig
+ IEzg+ zE
zg
+ IA
Ig
+ IA
zg
+ IEzg
~ 3 x IA
Ig
+ 3A
Ig
+ 5A
Ig
+ IA
zg
+ 2 x 3A
zg
+ 3 x IE
zg
+ 2 x zE
zg.
SOLUTIONS 8
8.1 Study Figure 8.27.
3350/(4 x 165.37 x 1.6605 x lO
z7)
= 1/a
3
; a = 0.690 nm; number of repeat units =
0.10 x 0.15 x 0.20 x 10
9/(0.690
x 10
9
) = 9 x 10
15.
8.2 Study Sections 3.3.2 and 8.3.
The combinations are
422422422422

422 422 422 422
Those involving one or three inversion axes are invalid symbols, because n n I = nil;
    
4 22 and 422 are equivalent, and the standard symbol is 42m; 42 2 is 4mm in
standard form. Thus, we have 422, 4mm and 4" 2m.
8.3 Study Section 8.3.
(a) Orthorhombic: ml.x; m1.. y; 2 along z.
(b) Hexagonal: 6 along z; 2 along x, y and u; 2 1.. x, y and u.
(c) Cubic: 4 alongx,y and z; 3 along <Ill>; m 1.. <110>.
(Note that <Ill> indicates the form of directions [111], that is, related by
symmetry. What are they in full?)
8.4 Study Section 8.4.
The problem involves twodimensional lattices.
(a) (i) 4mm,
(ii) 6mm;
(b) (i) Centring leads to a smaller unit cell with no change in symmetry; a
'
= al2 
b/2, b' = al2 + b/2.
(ii) Symmetry at each point is degraded to 2mm.
8.5 Study Section 8.4.
Monoclinic, 21m; r31 2" = 3a + b  2c; (r31 2" i = 9a
z
+ b
Z
+ 4c
z
+ [2 x 3 x (2)ac
cos(l200»); r31 2" = 2.58 nm.
8.6 Study Section 8.4.
Ensure righthanded axes and an obtuse p.
Tutorial Solutions 387
(a) a' = a, b' = b, c' = a/2 + c/2: if Ii' (c'? a') is now acute, take c' = al2 + el2 (see
Figure S8.1).
(b) a' =e, b' = b, c' = a.
(c) a' = a + c, b' = b, c' = a; if Ii' acute, take a' = a + c (see Figure S8.2).
(d) a' = a, b' = b, c' = a/2 + cl2; if Ii' acute, take c' = al2 + el2 (see Figure S8.3).
Fig. S8.1 Monoclinic B =monoclinic P.
Fig. S8.2 Monoclinic I =monoclinic C.
Fig. S8.3 Monoclinic F =monoclinic C.
388 Tutorial solutions
Fig. S8.4 Monoclinic C * monoclinic P.
(e) a' = al2 + b/2, b' = al2 + b/2, c' = c gives a P unit cell: but y' * 90°, so the C
unit cell is a monoclinic cell, different from monoclinic P (see Figure S8.4).
8.7 Study Section 8.4.
It is not an eighth system because the symmetry at each lattice point is no higher
than 1 ; it is a special case of the triclinic system with y = 90°.
8.8 Study Sections 8.4 and 2.5.2.
V= 0.7
3
[1  3 cos
2(109.47°)
+ 2 cos
3(l09.47o)]1/2
= 0.2640(4) nnr'. a/
2
= (b + c)·(b
+c) = a
2
+ a
2
+ 2a
2
cos(l09.47°) = 0.8082(9) nm. Cosia'ob') = (b + c)·(a + C)/o'2 =
a
2[3cos(109.47°)
+ 1]/0'2 = 0, so that y' = 90° (= a.,' = /3'). The transformed unit cell
is cubic, I, a' = 0.8082(9) run, V = 0.5280(8) nm' (= 2V
3
) ; point symmetry m3m.
(Confirm the I unt cell through Section 8.4.4.)
8.9 Study Section 8.4.5 and Figure S8.5.
An F cubic unit cell of side a has 12 lattice points distant a/"';2 from any given
point. Bisecting these lengths by planes leads to a rhombic dodecahedron that
encloses the single, given lattice point (See also Problem 3.22).
Fig. S8.5 WignerSeitz cell from an F cubic unit cell,
Tutorial Solutions 389
8.10 Study Sections 8.6.1 and 8.6.2.
(a) Monoclinic, 21m. C centred unit cell; 2 II y along [0, y, \I.], c glide ..1 y at (x, 0, z).
(b) Orthorhombic, mm2. Primitive unit cell; c glide..l x at(\I., y, z), a glide ..l y at (x,
0, z), 2
1
II z along [0, 0, z].
(c) Orthorhombic, mmm, Primitive unit cell; b glide .Lx at (\I., y, z), c glide .Ly at
(x, \I., z), a glide .Lz at (x, y, \I.).
(d) Tetragonal, 4mm. Primitive unit cell: 4 II z along [0, 0, z], b glide .L x at (1;4, y,
z) [and a glide..ly at (x, 1;4, z)], 2 II [110] along [!n, !n, 0] (and 211 [110] at [\12, !n,
0)).
8.11 Study Sections 8.6, 8.6.1 and 8.6.2.
{citeD, 0, ~ ) } ;
{41°}r =
r/.
,
[ ~  ~  ~ 1[: 1+ [ ~ 1= [ ; 1
[ ~  ~ n[: 1+ [ fl = [ ~ ~ z 1
(4 acts on this cglide plane to give a symmetryrelated cglide plane at x = 0.)
The product c 4 gives the third symmetry operator in the space group:
The product defines 2 along the line [x, x. lit] (and a symmetryrelated 2 along [x, 
x, lit)): space group P4c2.
8.12 Study Section 8.6.
In extenso, {Rlt}"r becomes [{Rlt}{Rlt},..{Rlt}{Rlt}]{Rlt}{Rlt}r, where the
expression in [ ] contains n 2 products. Hence, we have
{Rltr.· = [{Rlt}{Rlt},..{Rlt}{Rlt}]{Rlt}{Rlt}r
= [{Rlt}{Rlt},..{Rlt}{Rlt}](RRr + Rt + t)
= [{RltHRlt},..{Rlt}{Rlt}]{R"12t}r, because Rt = t.
Continuing the multiplication process:
{Rlt}" r = [{Rlt}{Rlt},..{Rlt}]{RltHR"\2t}r
= [{RltHRlt}...{Rlt}](R
3r
+ 2Rt + t)
= [{Rlt}{Rlt},..{Rlt}]{R
3[3t}r.
390 Tutolial solutions
It follows for all n repetitions of this process that
{Rlt}" r = {R"lnt}r.
Thus, n operations of a screw axis n
p
are equivalent to the rotation n, plus a
translation repeat along the direction of the axis. Thus, the possible screw axes are
given by the sum of (n  1) for n = 1, 2, 3, 4 and 6 (see Table 8.6).
8.13 Study Section 8.6.2 and Figure S8.6.
The Seitz operators are {blt(O, Y2, On, {alt(Y2, 0, O} and {mIO}. We expect 8 general
equivalent positions, from the planes .1 x, y and z.
For the b glide:
o
1
o
For the a glide:

and from the point x, Y2 +y, z, this matrix gives Y2  x, Y2  y, z. For the m plane:
   
and from the other three points this matrix gives x, Y2 + y, z, Y2 + x, y, z
and Y2  x, Y2  y, z. Collating:

x, y, z; x, Y2 +y, z; Y2 + x, y, z; Y2  x, Y2  y, z;
 
x, y, z; x, Y2 +y, z; Y2 + x, y, z; Y2  x, Y2  y, z.
Multiplication of the three symmetry operations (mab) or, more simply, by
comparing the points x, y, z and Y2  x, Y2  y, ~ , shows that i is at Y2, Y2, o. We
transform the origin to this point.
Tutorial solutions
~ : : "I
I ICD+ I
I 1 I
c__ r  r.L ._
1rT\ I 1fT\
1\1)+ 0 I 0 :\1)+
I CD+I 1
I 1 1
~    ~          I          ~    ~
CD
I , CD I
 . +1 0 I 0  '+1
: :(])+ :
~    r          L          ~    ?
1 CD I 1
,' + 1 ICD+
I 1 1
I 1 1
~ ~ ~
391
Fig. S8.6 Symmetry elements and general equivalent positions for space group Pbam, origin
on 1 (21m).
Let Xo =x  1f4, Yo =Y  1f4, Zo =z. Then, we obtain:
  
Xo , Yo, Zo; X
o,
Yo, Zo; Y2 +x
o
, Y2  Yo, zo; Y2  XO, Y2 +Yo, zo;
   
X
o,
Yo, zo; xo,Yo, z 0; Y2  xo, Y2 +Yo, Zo; Y2 + XO, Y2  Yo, Zo,
which, dropping the subscripts, are the general equivalent positions for Pbam with
the origin on i (see Figure S8.6). From the coordinates, we can see, for example,
that the symmetry axis normal to the a glide plane is 2
1
along [x, 1f4, 0], and so on;
. P 2 2 2
the full symbol for the space group IS ....l.. ....l..  •
bam
8.14 Study Section 8.6.2 and Figures S8.7 and S8.8.
Take 4 along 0, 0, 0, n glide at (P, y, z) and c glide at (q, q, z):
{410}, {nlt(2p, Y2, Y2)}, {clt(q, q, z)}.
[Note that an nglide plane exists also at (x, p, z) and a cglide plane also at (q, q,
z).]
In Figure S8.6, point P(x, y) is reflected across the m plane to Q(x, y'); the z
coordinate is unchanged. From the geometry of the diagram, we have:
oe = ow= q, so that ewis at 45° to the x and yaxes.
x' =OB =oe Be =oe BR =q  y;
y' = OV= ow VW= ow VS= q x.
[
1
a
a
392 Tutorial Solutions
I
I
I
I
P x,y)
I
,'$
I
. I
,
I.
I
'R
Q(x' ,y')
,
1'""....
,
m plane
,
I
o
A
B
c
u
t X axis
v w
7
Y axis
c
Fig. 88.7 Justification of x, Y, z ~ q  y, q  x, z in P4nc.
From 4:
From second and third operations, we obtain x, y, z and y, x , z.
From n:
From the other three points, we generate 2p + x, Y2  y, 1'2 + Z, 2p  y, 1'2  x, Y2 + z,
2p +y, Y2 + x, 1'2 +Z.
From c:
We need not generate any more points from this matrix: we expect only eight
general equivalent positions, and we know that n4 == c. Thus, 2p  y, Y2  x, Y2 + Z
and q  y, q  x, 1/2 + Z are one and the same point, so that q = 1/2 and p = q/2 = 1/4
(see Figure 58.7).
O
0+
+
Tutorial Solutions
0+
I 'l" 1+0
I .·r·. I / 0+
+0 '. ' , ;1'0
, I .' . 1/
 
i 1''''0 ./ i
'"2., 0,(.1'
I •  I
1... 2 T
1
  _
. 2 / f.')"r. 2., .•'
. I' V 2 1 .'
 
• I"' ." I"
O
O,/ ! ····. '!'O" 0
t I ". I + "
0+ I I
+0
Fig. 58.8 Space group diagram for P4nc, ongin on 4.
8.15 Study Section 8.7.
393
mmm )
2h
Pbam
E
1
c (z ) C (y) c (x ) i
222
222 1
1 1
a(yx) a(zx) a(yz)
m a b
With a onetoone correspondence between mmm (D
2h
) and the factor group for
Pbam, the character table for D
2h
(Appendix 11, A11.1) is appropriate for use with
this group.
0+
Fig. 58.9 Transformation of Pc to PII.
0+
0+
8.16 Study Section 8.4ffand Figure S8.9.
The transformation a' == c. b' == b, c' == a converts Pa to Pc. The transformation a' ==
a, b' == b. c' == a + c converts Pc to Pn (see Figure S8.9. In the case of Ca, the
centring introduces translations along a and h so that the m planes normal to yare
interleaved by a glide planes. Cc is different because the c glide introduces a
translation along c. However, the C centring gives rise to interleaving n glide
394 Tutorial Solutions
planes, translation (a + c)/2, so that Cc= en. The reader should make drawing of
these centred space groups.
8.17 Study Section 8.6.2.
4 1
1 1 1 1
X, y, z' x, y, z' x,   y,  + z; x,  + y,  
z. , ,
2 2 2 2
2 1
1
0,
1 1 1
a 
 
2 '
2' 2' 2'
2 1 0, 0,
1
0,
1
a 
2' 2' Four sets of special
2 1
1
0, o·
1 1 1
equivalent positions.    
2'
,
2' 2'
2
2 1 0, 0, o· 0,
1 1
  ,
2'
2
8.18 Study Section 8.6.
{4
1
It (0, 0, 1!4}; x, y, z ~ y,x, If.t + z; the inverse operator is 4
3
:

{4
3
It (0, 0, 7'4}; X, y, Z ~ y, x , % + z. It follows that
= HIO}.
8.19 The oblique stroke in the symbol indicates perpendicularity, so that mmm
perpendicular to 4 (or 6) is meaningless. This symbolism obscures the fact that each
position in a HermannMauguin symbol gives symmetry information about one
direction, that is, along an axis and/or normal to it.
8.20 Study Sections 4.1.2,4.4,6.3.5,8.7 and 8.8.
(a) Two molecules in P2Jm must lie on either I or m. Since the molecule cannot be
centrosymmetric its symmetry is m, which is also the site symmetry. (b) The factor
group is 21m (C
2I
J (c) The symmetry of the M(CO)3 moiety is 3m (C
3v
) . (d) The
representation is
2
1
o
1
6
21m 1
f
rod
which reduces to 2Ag + B
g
+ Au + 2B
u.
(e) From the direct products A
g
0 (;J 0
2A
g
(B
g
, Au, 2B
g
) , we find infrared activity in Au and 2B
u.
From the direct products
Tutorial Solutions 395
A
g
l8l (;:) l8l 24
g
(B
g
, Au, 2B
u
) , we find Raman activity in A
g
and 2B
g
• (f) The
infrared and Raman bands are noncoincident, because the crystal is
centrosymmetric.
REFERENCES AND SELECTED READING
References numbered in the text
[1] M.F.e. Ladd and RA. Palmer, Structure Determination by XRay Crystallo
graphy, 3rd Edition (Plenum Press, 1994).
[2] S.L. Altmann, Icons and Symmetries, (Oxford University Press, 1992).
[3] W.A. Bentley and W.J. Humphreys, Snow Crystals, (McGrawHill, 1931).
[4] 1. Kepler, The SixCornered Snowflake, (Clarendon Press, 1966); published
originaIly, in Latin, as A New Year's Gift, or On the sixcornered snowflake
(1611).
[5] C.H. Macgillavry, Symmetry Aspects of M C Escher's Periodic Drawings,
(Oosthoek's Uitgeversmaatschappij, 1965).
[6] 1. Rosen, Symmetry Discovered, (Cambridge Universitry Press, 1975).
[7] International Union of CrystaIlography, International Tables for
Crystallography, Volume A (Reidel, 1983); formerly International Tables for
XRay Crystallography, Volume 1 (Kynoch Press, 1965).
[8] M.F.C. Ladd, Symmetry in Molecules and Crystals, (EIlis Horwood, 1992).
[9] A.e. Aitken, Determinants and Matrices, (Oliver and Boyd, 1964).
[10] C.M. McGregor, J J C Nimmo and W W Strothers, Fundamentals of University
Mathematics, (Albion Publishing, 1994).
[11] H.S. WiIf, Mathematicsfor the Physical Sciences, (Wiley, 1962).
[12] RS. MuIliken,.J. Chern. Phys. 23, 1997 (1955).
[13] L. Euler, Akademia nauk Leningrad, 4, 109 (1752).
[14] M.F.e. Ladd, Int. J. Math. Ed. in Sci. and Tech. 7,395 (1976).
[15] R McWeeny, Symmetry, (Pergamon, 1963).
[16] H. Eyring, J Walter and G E Kimball. Quantum Chemistry (Wiley, 1944).
[17] D.M. Bishop, Group Theory and Chemistry (Clarendon Press, 1973).
[18] G.G. Hall, Appied Group Theory (Longmans, 1967).
[19] L. Pauling and E.B. Wilson, Introduction to Quantum Mechanics (McGraw
Hill, 1935).
[20] M.F.e. Ladd, Chemical Bonding in Solids and Fluids (EIlis Horwood, 1994).
[21] 1.N. Murrell, S.FA Kettle and 1.M. Tedder, Valence Theory, 2nd Edition
(Wiley, 1969).
[22] A. Streitweiser. Molecular Orbital Theory for Chemists (Wiley, 1961).
[23] F.C. Phillips, An Introduction to Crystallography (Macmillan, 1971).
[24] H. Eyring, 1. Walter and G.E. Kimball, Quantum Chemistry (Wiley, 1963).
[25] 1.e. Slater, Quantum Theory of Molecules and Solids, Volume 1 (McGraw
HiIl, 1963)
[26] A.D. Walsh,.J. Chem. Soc. 2250 (1963).
[27] RB. Woodward and R. Hoffmann, Angew. Chem. 8, 781 (1969).
[28] P.W. Atkins and R.S. Friedman, Molecular Quantum Mechanics, 3rd Edition
(Oxford University Press, 1997)
[29] G. Herzberg, Atomic Spectra and Atomic Structure (Dover, 1944).
[30] M. Karplus and R.N. Porter, Atoms and Molecules (Benjamin, 1970).
[31] B.N. Figgis, Introduction to Ligand Fields (Wileylnterscience, 1966).
[32] S.F.A. Kettle, Physical Inorganic Chemistry (Spektrum, 1996).
References and selected reading
397
[33] M. Orchin and H.H. Jaffe, Symmetry, Orbitals and Spectra (Wiley
Interscience, 1971).
[34] L.E. Orgel, An Introduction to TransitionMetal Chemistry: Ligand Field
Theory (Wiley, 1966).
[35] E.B. Wilson, r.c Decius and P.e. Cross, Molecular Vibrations (McGrawHill,
1955).
[36] L.A Woodward, Introduction to the Theory of Molecular Vibrations and
Vibrational Spectroscopy (Oxford University Press, 1972).
[37] T.R Gilson and PJ. Hendra, Laser Raman spectroscopy (Wiley, 1970).
[38] P.W. Atkins, Physical Chemistry (Oxford University Press, 6th Edition, 1998).
[39] 1.e. Decius and R.M. Hexter, Molecular Vibrations in Crystals (McGrawHill,
1978)
[40] AR West, Solid State Chemistry (Wiley, 1984)
[41] e.N. Banwell, Fundamentals ofModern Spectroscopy (Van Nostrand, 1960).
[42] M.F.e. Ladd,.J. Chem. Educ. 74. 461 (1997).
[43] E. Wigner and F. Seitz, Phys. Rev. 43,804 (1933)
[44] S.F.A Kettle, Symmetry and Structure (Wiley, 1995).
[45] 1.S. Rollett, Computing Methods in Crystallography (Pergamon, 1965).
[46] G. Bums and AM. Glazer, Space Groups for Solid State Scientists (Academic
Press, 1978).
[47] e.H. MacGillavry. in MiC. Escher: Art and Science edited H.S.M. Coxeter
(Elsevier Science, 1986).
[48] N.N. Belov, N.N. Neronova and T.S. Smirnova, SOl'. Phys. Crystallogr. 2, 311
(1957).
[49] AV. Shubnikov and N.V. Belov, Coloured Symmetry (Pergamon, 1964).
[50] AR West, Solid State Chemistry and its Applications (Wiley, 1984).
[51] S.FA Kettle and LJ. Norrby,.J. Chem. Educ. 67, 1022 (1990).
[52] M.F.e. Ladd, Introduction to Physical Chemistry, 3rd edition (Cambridge
University Press. 1998).
[53] M.F.e. Ladd, Structure and Bonding in Solid State Chemistry, (Ellis Horwood,
1979).
[54] 1.H.Van Vleck, The Theory of Electric and Magnetic Susceptibilities (Oxford
University Press, 1965).
[55] RL. Carlin, Magnetochemistry, (SpringerVerlag, 1985).
[56] M.L. McGlashan, PhysicoChemical Quantities and Units, Monographs for
Teachers, Number 15 (Royal Society (formerly Institute) of Chemistry, 1968).
[57] P.W. Atkins, M.S. Child and e.S.G. Phillips, Tables for Group Theory (Oxford
University Press, 1970).
[58] D.C. Harris and M.D. Bertolucci, Symmetry and Spectroscopy (Oxford
University Press, 1978).
[59] RS. Halford,J. Chem. Phys. 14, 8 (1946).
[60] L. Couture,J. Chem. Phys. 15, 153 (1947).
[61] R.L. Carter, JChem. Educ. 48.297 (1971).
[62] E.S. Federov, Symmetry of Crystals, American Crystallographic Association
Monograph 7, (A e. A 1971).
398
References and selected reading
Further selected reading
CJ. Bradley and A.P. Cracknell, The Mathematical Theory of Symmetry in Solids
(Clarendon. 1972).
F.A. Cotton, Chemical Applications ofGroup Theory, 3rd Edition (Wiley, 1990).
G. Davidson, Group Theory for Chemists (Macmillan. 1991).
RL. DeKock and H.B. Gray, Chemical Structure and Bonding (University Science
Books, 1989).
R Drago, Physical Methods in inorganic Chemistry (Reinhold, 1965).
M. Gerloch, Orbitals, Terms and States (Wiley, 1986)
L.H. Hall, Group Theory and Symmetry in Chemistry (McGrawHili, 1969).
E. Heilbronner and H. Bock, The HMO Model and its Application, Volume 1,
(Wiley, 1976).
M.A. Jaswon, Mathematical Crystallography (Longmans, 1965).
G.F. Koster, 1.0. Dimmock, RG. Wheeler and H. Statz, Properties of the Thirty
two Point Groups (M. I. T Press. 1963).
H. Margenau and G.M. Murphy, The Mathematics of Physics and Chemistry (van
Nostrand, 1943).
C. McGregor, 1. Nimmo and W. Stothers, Fundamentals of University Mathematics
(Albion Publishing, 1994).
R McWeeny, Symmetry (Pergamon Press, 1964).
C.E. Moore, Atomic Energy Levels, Volumes I, 2 and 3 (NBS Circular 467 1949,
1952 and 1958).
A. Nussbaum, Applied Group Theory for Chemists. Physicists and Engineers
(prenticeHall, 1971).
L. Pauling and E.B. Wilson, introduction to Quantum Mechanics (McGrawHill,
1935).
AJ.Pettofrezzo, Vectors and Their Applications, (PrenticeHall, 1966).
D. Schonland, Molecular Symmetry (Van Nostrand, 1965).
Index
A1temant hydrocarbon, 152
Ammonia, 76, 231
Anglebend vibration modes, 223
Angular momentum
combined, 188, 218
orbital, 187
spin, 187
Anharmonicity,229
Anisotropy, 3
AntiStokes radiation, 226, 230
Antisymmetry, 117
AO (see Atomic orbital)
Asymmetric centre, 19
Asymmetric unit, 269
Asymmetry, 20
Atomic orbital, 83, 130, 133,313
p,317
d, 318
Aufbau principle, 141, 149, 195
Axes
crystallographic reference, 249
interchange of, 321, 327, 332
orthogonal, 18,20
reference, 18
selection of, in molecule, 18
rotation, intersection of, 59
Barium titanate, 281
Basis vector, 73, 76
Bendmode, frequencies (energies) of, 233, 235
Benzene, 144ft: 217, 220, 231
blockfactored matrix for, 147
molecularorbital energylevel diagram for, 150
7tmolecular orbitals for, 148, 149
polynomial equation for, solution of, 145
secular determinant for, 144, 147
symmetryadapted orbitals (SALCs) for, 146
use of projection operator for, 146
use ofpure rotation group for, 145
Bideuteromethane,239
Biphenyl, 280
properties of, from spacegroup data, 280
Bohr magneton, 214
Bohr radius, 128
Boltzmann distribution, 229
Bond order
mobile, 150
7t, 149
total, 142
Bondstretch vibration modes, 223
Bonding overlap, 138
Bonding power, total, 217
BornOppenheimer approximation, 108
Boron trifluoride, 223
Bravais lattices, 59, 252ff
the fourteen, 254,255
unit cells of, 59 (see also Lattice unit cell)
building up of, 256ff
ButaI,3,diene, 106, 182ft; 314
Carbon dioxide, 239
Carbonate ion
7tbonding in, 142
symmetryadapted orbitals for abonding in, 123ff
Centre of symmetry, 16, 131,273
Centred unit cell, 254
CFSE (see Crystalfield stabilization energy)
Changeofhand, 20
Character, 88
Character table, 87ff
construction of, 97ff
partitioning of, 99, 103
redundant data in, 332
validation of, 98
Character tables, 319ff
Characteristic equation, 29
Charge distribution, 152
Chargetransfer spectra, 212
Chirality, 19
ClebschGordan series, 188, 243
Closed angle set, 225
Closure, 38
Cofactors, 27
Column, 73
Combination bands, 236
Commutation, 27, 39
Complex characters, 90,126,331
Computer programs, 339
Concerted reaction, 182
Conjugate characters, 331
Conrotatory mechanism, 183
Correlation, 183
Correlation diagrams, 197ft'
Correlation tables, 332ff
Coset, 43
Coulomb integral, 134, 143
Coupling (see RussellSaunders; JJ)
Crystal class, 249
Crystal symmetry, 248
levels of, 248
Crystal systems, minimum symmetry of, 248
table of, 248
Crystal
perfect, 4
real, 3
Crystalfield energy, 195
Crystalfield stabilization energy, 195
Crystalfield stabilization energies, table of, 196
Crystalfield theory, 186ff
Cube, 59
Cubeoctahedron combination, 59
Cubic lattices, 261
Cubic structures, 280
Curie law, 214
Cyclization, 182ft: 220
Cyclobutene, 182
Cylindrical symmetry, 313
d +d Transition, 245
Dmatrix, 74
Degeneracy, 109, 115
Degenerate states, electron transitions among, 243
Degree of freedom, 221
Delocalization, 130
energy, 149
de Moivre's theorem, 193,331
Depolarization, 232
Descending symmetry, method of, 199if
Determinant, 23if
blockfactored, solution of, 155
minor of, 24
numerical value of, 24
Diagonalization, 30
Jacobi method for, 31, 32
Diamagnetism, 213
Diatomic molecule (see also Homonuclear), 228
DielsAlder reaction, 220
Dihedral angie, 297
Dipole moment, 156, 169,226,242
vector, 226
Dipole
induced, 230
oscillating, 226
Direct product, 54, 227, 230, 319, 320
uses of, 104
use ofoperators with, 115
Direction cosines, 291, 302
Direction, 252, 343
Disrotatory mechanism, 183
Dissociation energy
experimental, 229
theoretical, 228
Dissymmetry, 20
Doublet, 190
Eigenenergy (see Eigenvalue)
Eigenfunction, 28
Eigenvalue, 28
Eigenvector, 28, 153
7tElectronapproximation, 142if
d Electron configurations, 188, 192
Electron density, 7, 168
probability of, 110, 130
Electron overlap, 280
Electron spin, 243
selection rule for, 243
Electron spins, combination of, 243
Electron transitions, 242if
Electrons
delocalized, 130
mutual interaction of, 132
Elongated rhombic dodecahedron, 59
Enantiomer, 1020
Enantiomorphism, 61
Energy levels
combined, 236
vibrational, 236
Energy
electronic, 109, 221
quantization of, 228
rotational, 221
vibrational, 221
Energysplitting parameter ~ 194
Equipoints (see General equivalent positions)
Euler, 60
construction of, 49
Even function, 6
Factor group, 282if
Factor group analysis, for iron(Il) sulfide, 282
Factor group method
correlation diagram in, 285
for potassium chromate, 284
Federov solid, 59
Fermi resonance, 236, 237
Fine structure, 175, 190
rotational, 241
Fivefold symmetry, 331
Force constant, 228, 229
Form, 250
Fourier series, 6
Fractional coordinates, 256
Free valence, 151
Frontier molecular orbitals, 149
Function
antisymmetric, 88
even, 131
fully (totally) symmetric, 88
odd, 132
symmetric, 88
Function space, Ill, 120
Fundamental transition, 226, 236
Fundamental vibration, 222
Gamma function, 312
Gases, vibrations in, 241
General equivalent positions, 64, 266
Glide planes, 267, 269, 282
notation for, 270
Great circle, 296
Great orthogonality theorem, 91if
special cases of, 92if
Ground state, 225
Group multiplication table, 40, 42, 88
Group theory, 38if
Group
Abelian, 39, 46, 263
abstract, 39, 41
commutative (see Group, Abelian)
conjugate members of, 44
cyclic, 40, 41
defmitions, 39, 40
finite, 39
homomorphic, 40, 75
identity member, 39
infinite, 39, 263
inverse member, 39
isomorphic, 40, 41
linear, 91
multiplication table, 40, 42, 88
order of, 39
postulates, 38
translation, 42
unit member (see Group, identity member)
Groups
associative law in multiplication of, 39
combination of, by addition, 41
combination of; by vector addition, 42
direct product of, 54
laws ofcombination for, 39
multiplication of; 39
Halftranslation rule, 274, 276
Halving, 266
Hamiltonian (see also Operator, Hamiltonian)
eigenfunctions of; 132
electronic, 131
fully symmetric representation with, 132
Harmonic oscillator, 228, 229
Harmonics, 222
HermannMauguin notation, 11,248,340,346
power of; 276
table of; 250
symmetry symbols for, positions in, 249, 250
Hexagonal prism, 59
Hexagonal system, 248, 343, 344
Hexanuninecobalt(III) chloride, 186, 188
crystalfield theory for, 192
Hexaquaovanadium ion, 197
Hexaquotitantium(III) ion, 212
Highspin compounds (see Weakfield compounds)
Highsymmetry point groups, 104
Hole formalism, 203, 204
HOMO (see Frontier molecular orbitals)
Homonuclear diatomic molecule, 135, 137, 142
Hiickel4n + 2 rule, 156
Hiickel molecular orbital method, 147ff
with heteroatorns, 157ff, 217
Hybrid orbitals, 167, 210, 316
symmetrical, 169
Hybridization, 167ff
Icosahedron, 60
Inplane vibration, 225
Infrared active vibration, 226, 227
Infrared activity, 235, 283
Infraredforbidden vibration, 226
Infrared spectra, general selection rule for, 226
Infrared spectroscopy, 226ff
Infrared, coincidence with Raman spectra, 285
Interaxial angles, 19
relationships of, 249
Intermolecular forces, 241
Internal coordinates, 234
for water, 222
Internet, 56, 339
Irreducible representations, multiplication of, 337
Isomorphism, 282
JJ coupling, 192
Jahn Teller distortion, 218
Jahn Teller theorem, 177
Kineticenergy operator, 108, 131
invariance of; 109
Koopman's theorem, 175
Kronecker delta, 21
Ladd symmetry notation, 344
Lande factor, 215
LangevinDebye equation, 214
Laplacian operator, 305
Laporterule, 211, 242
breakdown of, 245
Lattice unit cell (see also Unit cell), 253
Lattice vibrations, 283
Lattice, 252, 253
onedimensional (see Row)
translation vectors in, 252
LeAO (see Linear combination ofatomic orbitals)
Ligandfield theory, 186
application to ML
6
complexes, 205ff
SALes for, 205ff
Linear combination ofatomic orbitals, 132
coefficients for, 133, 137, 155,314
method for oxygen, 137
Linear combination, theorem of, 109
Linear independence, 111,316
Linear molecule, 222
representation for, 239
vibrational modes for, 240
Lone pair, 169
Lowspin compounds (see Strongfield compounds)
LS coupling (see RussellSaunders coupling)
LUMO (see Frontier molecular orbitals)
Magnetic dipole moment (see Magnetic moment)
Magnetic flux density, 213
Magnetic moment, 5, 187, 213
spinonly contribution to, 215
Magnetic moments, table of, 216
Magnetic susceptibility
mass, 213
volume, 213
Magnetization, 213
Magnetogyric ratio, 214
Matrices
addition of, 25
conjugate, 31
direct product of, 86, 104
equal, 25
isomorphic, 96
multiplication of, 26, 75
associative and distributive laws in, 26
product of, inverse for, 27
subtraction of, 25
Matrix, 20ff
adjoint, 34
blockfactored, 33, 80, 81, 95, 209
blocked (see Matrix, blockfactored)
character of (see Matrix, trace of)
cofactor, 24
columns of, 23
conjugate, 34
diagonal terms of, 23
diagonaliziation of, 302
dimensions of, 92
Hermitian, 34
identity, 29
inversion of, 27
nonsingular, 27, 30
onecolumn, 23
orthogonal, 28, 302
partitioned, 86
properties of, summary for, 35
real, 34
rotation (see Rotation matrices)
rows of, 23
singular, 27, 28
square, 23
synunetric, 25, 28,32,302
term, cofactor of, 24
trace of, 23
transpose of, 25
unitary, 35
173,316
LCAO method for, 165
SALCsfor, 166, 173
synunetry elements of, 165
Methylenecyclobutene, Hiickel method for, 153
Methylenecyclopropene, Hiickel method for, 153
Miller indices, 3
Minimumenergy conformation, 280
Mirror image, 3
ML
6
compound, energylevel diagrams for, 210ff
(see Molecular orbital)
Molecular orbital, 130
antibonding, 131, 140
bonding, 131, 140
energylevel diagram, 141
theory, 130ff
Molecular orbital method, approximations in, 132ff
Molecular orbitals, building up of, 140
classification ofby synunetry, 130
notation for, 141
Moment ofinertia, 222
Monodeuteromethane, 238
Morse equations, 228
Multidimensional space, 92, 115
Multiplicity, 189, 197, 199
Mutual exclusion rule, 232
n Transition, 243
lIfaphthaIene,241,280
1Ifet, 252
Neutron diffraction, 5
Nodal plane, 130, 164
IIfonalternant hydrocarbon, 152
Noncrossing rule, 183
extension of, 202
Nonsymmorphic space groups, 272ff
monoclinic, 272
orthorhombic, 275
in class 222, 275
in class mmm, 276
tetragonal, 278
Nontranslational synunetry elements, 266
Normal modes, 222
synunetry of, 222
Normalization, 147,315,332
Odd function, 6
Operator, 12
Hamiltonian, 108
commutation of, 109
differential, 12
dipole moment, I 18
linear, 12
projection (see Projection operator)
transformation, 112, 132, 307, 3IO
transformation, rules for, I 12
transitional moment, I 18
unitary, 113, 114
Operators, linear, properties of, 12
Optical activity, 19
(J Orbital 130
It Orbital
Orbital angular momentum (see Angular
momentum, orbital)
Orbital energy levels, 174
Orbital ionization energies, table of, 177
d Orbitals
rotation diagram for, 209
vector diagram for, 206, 208
Orgel diagram, 21 I, 212, 218
Orthogonality, 28, 89
Orthonormality, 89,167, 180
Outofplane vibration, 225
Overlap bonding, 134
Overlap integral, 128, 134, 143,217,313
Overtone band, 236
Overtones, 236
Paramagnetism, 142,213
Parity, 242
Pauli exclusion principle, 133, 192
Pentailuoroantimonate ion, LCAO method for, 163
Pentagonal dodecahedron, 60
Phonon
acoustic, 283
optic, 283
Phosphorus pentachloride, 233
Photochemical reaction, 183
Photoelectron spectra
hydrogen atom and hydrogen molecule, 175
nitrogen and oxygen molecules, 176
Photoelectron spectroscopy, 174ff
Photon, 226
absorption of, 236
Planepolarized light, 19
Plato solid, 59
Point groups, 38ff
Abelian, 88,90
building up of, 52ff
crystallographic, 248
crystallographic, stereograms for, 65
derivation of, 46ff
dihedral, 52
direct product of, 100
homomorphic, I 12
octahedral, 52
practical recognition of, 6I
tetrahedral, 52
summary of, 56
Pointgroup recognition programs, 341, 342
Polar coordinates, 84
Polar triangle, 50, 298
Polarizability, 230
Polarizability tensor, 230
Pole, 295
Polygon, regular, 59
Position vector, 73, III
Potential energy, 228
operator, 108, 131
invariance of; 109
Primitive circle, 295
Primitive unit cell, 253
Primitive, 295
Principal axis, 18,319
Programs (see Computer programs)
Projection operator, 119ff, 154, 316
Pyridine, 157ff
bond orders for, 160, 161
charge distribution for, 161
delocalization energy for, 161
dipole moment for, 162
eigenvalues for, 160
eigenvectors for, 160
free valences for, 160, 161
Huckel molecular orbital method for, 157
Jacobi diagonalization for, 159
matrix for, blockfactored, 159
molecularorbital energylevel diagram for, 162
projection operator for, 158
secular determinant for, 159
Quantum numbers, 187
Radiation quantum (see also photon)
Radii, ionic, 281
Raman activity, 230, 235, 283
Raman spectra
general selection rule for, 230
polarization of; 232
Reduced mass, 229
Reduction formula, 312, 313
Redundant mode (see Spurious mode)
Repeat mechanism, 4
Repeating pattern, 4
Representation reducible, frequency of; 97
Representation, 73ff
degenerate, second function for, 125
fuIJy (totally) symmetric, 85, 117
irreducible, 81
antisymmetric character of, 90
symmetric character of, 90
on atom vectors, 79
on basis vectors, 76
on direct product functions, 85
justification for, 116
on functions, 83
on position vectors, 73
onedimensional, 89
reducible, 81
reduction of, 95
threedimensional, 89
twodimensional, 89
unshiftedatom contributions to, 82
table of, 83
Representations
equivalence of, 78
irreducible, notation for, 89
rule for construction of; with functions, 124
Resistors, symmetry framework of, 8
Resonance energy (see Delocalization energy)
Resonance integral, 135, 144
Resonance integral, 144
Rhombic dodecahedron, 59
Rhombohedral lattice, 344
Rotation axes, permitted angles between, 53
Rotation matrices, 343
Rotation
improper, 17,52
proper, 17, 52
sign of, 15
Rotational movement, 88
Row, 73, 252
RusseIJSaunders coupling, 188
SALe (see Symmetryadapted linear combination)
Scalar,20ff
SchOnflies notation, 11,248,340,345
power of; 71
SchrOdinger equation, 108, 131, 228
for harmonic oscillator, 6
timeindependent, 108
Screw axes, 268, 282
generalized, 269
notation for, 271
Secular determinant, 135, 153
general,137
Secular equations, 135, 314
generaql, 137
Seitz operators, 264, 272, 282
rules for, 264, 265
symbols for, 276
Selection rule, 191
Selfconsistent field approximation, 132
Sidebyside overlap, 139
Similarity transformation, 31, 44, 46, 78, 96, 126
Singlet, 189, 199
Sitegroup analysis, 284
for potassium chromate, 284
Sodium chloride, 280
Solids, vibrations in, 241
Solutions (see Tutorial solutions)
Space group, 39, 248
translation vector in, 264
Space groups, 264ff
applications of; 280ff
signchange rules for, 277
symmorphic, 265ff
nonsymmorphic, 272ff
Spanning, 88, 230
dependence on choice ofaxes, 88
Special equivalent positions, 64, 266, 272, 280
Spectrochemical series, 194
Spectroscopy, transitions in, 117
Spherical harmonic, 187, 192
Spherical polar coordinates (Polar coordinates), 305
volume element in, 305
Spherical projection, 49, 294
Spherical triangle, 297
formulae for, 297
Spherical trigonometry, 297ff
Spheroidal coordinates, 313
volume element in, 313
Spin angular momentum (see Angular momentum)
Spin function, 187
Spin multiplicities, direct products of, 338
Spin selection rule, 211
Spinallowed transition, 245
Spinorbit coupling, 212
Spurious mode, 225, 234
Squareplanar configuration, 202
Stacking, 4
Starred atoms. 152
Stereogram (see also Stereographic projection), 294
notation for, 300
examples of, 299
Stereographic projection, 294ff
Stereoscopic view, 2
Stereoview, 288
Stereoviewer, 288
construction of, 288
Stokes radiation, 226, 230
Stretchmode, frequencies (energies) of, 233, 235ff
Strongfield (lowspin) compounds, 194
Structure unit cell (see also Unit cell), 253
Subgroup, 40, 43,332
invariant, 43
order of, 43
Sublimation energy, 197
Submatrix, 33, 95
Successive elimination, method of, 314
Sulfur hexafluoride, 178ff
generation ofsecond E function for, 180
hybrid orbitals for, 180
LeAO method for, 179
molecularorbital energylevel diagram for, 182
orbital energy levels for, 181
p orbitals and d orbitals in, 178, 179
SALes for, 180, 181
Supergroup, 40
Symmetry ascent, technique of, 283
Symmmetry
alternating axis, 15
apparent, 3
approach to, 9
class, 44
dependence on probe, 5
elements, 11, 12
conceptual nature of, 13
combination of, 3,4
combined action of, 16
identity, 17
inversion, 16
notations compared, and example compounds, 67
notations for, 11, 18, 248, 340, 346
operations, 5, 11
combination of, 18, 47
multistep, 14
plane of, 2, 15
practical definition of, 5
reflection, 2, 6, 15
requirement of, 4
rotational, 13, 248
in Bravais lattice, 260
rotoinversion, 17, 248
rotoreflection, 15,248
S4axis, model with, 289
teaching of, 346, 347
translation, 6
Symmetryadapted linear combination, 119ff
Symmetryadapted orbitals, orthonormality of; 124
rule for construction of, with lower symmetry, 125
Symmetryallowed spectra, 244
Symmetryforbidden spectra, 212, 241, 244
Term symbols, 186ff
Tetrachloromethane, Fermi resonance in, 238
Tetradeuteromethane,239
Thermal reaction, 183
Threecentre bonding, 218
Transformation ofaxes, 292, 302
Transition
n ~ 0'*,243
d ~ d, 245
Transition moment, 226
Transitionmetal compounds, 186ff
electron transitions in, 244
magnetic properties of,213ff
spectral properties of, 211
Translation group, 42, 263
vector addition in, 263
Translational movement (displacement), 88
Trideuterornethane,239
Trigonal bipyramid, 234
Trigonal system, 248, 249
Trigonal system, 249
Trimethylarmnonium chloride, 282
Triplet, 199
Tutorial solutions, 348ff
Unique lattice points, 256
Unit cell, 253ff
bodycentred cubic, 5
bodycentred, 263
translation group for, 263
for lattice, 253
for structure, 253
number of molecules in, 280
primitive, 5
rhombohedral, 261
translation, 261
Unit vector, 21, 73
Unitary representation, 307
from orthonormal basis, 307
Unitary transformation (see Unitary representation)
Unshifted atom, 223, 283
Unstarred atoms, 152
Vanishing integral, 117,226,230,242,
Variation principle, 133ff
Vectors, 20ff
cross product of, 21
dot product of, 20
Vibration spectra, correlation tables with, 239
Vibration, fully symmetric, 232
Vibrational energy, 176
Vibrational modes, classification of, 233
Vibrational quantum number, 175
Vibronic coupling, 212
Volume ofparallelepipedon, 21, 259
Walsh diagram, 172
Water, 74, 82, 167,227,233,242
bonding orbital for, 170, 171
lone pair orbital for, 170, 171
molecularorbital energylevel diagram for, 172
Wavefunetion, 108
atomic, spatial part of, 133
Born probability interpretation of, 110
ground state, for hydrogen, 132
normalization of, 110
oneeleetron, 186
properties of, 110
real, 133
vibrational, ground state form of, 118,227
Weakfield (high spin) compounds, 194
WignerSeitz cell, 59, 262
properties of, 261
WoodwardHoffinan rules, 182
Wyckoffnotation, 280, 283, 284
Xray diffraction, 5
Zeeman effect, 214
Zeropoint energy, 221, 228
Zone, 296
Zone axis, 296
Zone circle, 296