Second Edition

Group Theory and

Its Applications
in Chemistry
A. Salahuddin Kunju
G. Krishnan
GROUP THEORY AND ITS APPLICATIONS IN CHEMISTRY
GROUP THEORY AND
ITS APPLICATIONS
IN CHEMISTRY
SECOND EDITION

A. SALAHUDDIN KUNJU
Formerly
Principal, University College, Thiruvananthapuram
and
Head, Department of Chemistry
University College, Thiruvananthapuram

G. KRISHNAN
Formerly
Principal, Government College, Chavara, Kerala
and
Head, Department of Chemistry
University College, Thiruvananthapuram

Delhi-110092
2015
GROUP THEORY AND ITS APPLICATIONS IN CHEMISTRY, Second Edition
A. Salahuddin Kunju and G. Krishnan

© 2015 by PHI Learning Private Limited, Delhi. All rights reserved. No part of this book
may be reproduced in any form, by mimeograph or any other means, without permission in
writing from the publisher.

ISBN-978-81-203-5134-9

The export rights of this book are vested solely with the publisher.

Third Printing (Second Edition) … … … August, 2015

Published by Asoke K. Ghosh, PHI Learning Private Limited, Rimjhim House, 111, Patparganj
Industrial Estate, Delhi-110092 and Printed by Mudrak, 30-A, Patparganj, Delhi-110091.
Dedicated to our
Teachers
Preface xi
Preface to the First Edition xiii

Part I Basic Principles of Group Theory

1. Molecular Symmetry 3–29
1.1 Introduction 3
1.2 Symmetry Elements and Symmetry Operations 3
1.3 Centre of Symmetry 4
1.4 Plane of Symmetry 5
1.5 Proper Axis of Symmetry 8
1.5.1 Principal Axis and Subsidiary Axes 10
1.5.2 Types of Planes of Symmetry 11
1.6 Improper Axis of Symmetry 12
1.7 Point Group 14
1.7.1 Crystallographic Point Groups 14
1.7.2 Non-crystallographic Point Groups 16
1.7.3 Why the Name Point Group? 16
1.8 Assigning Point Groups 16
1.8.1 Illustrative Examples 17
1.9 Symmetry Operations and Order of a Group 20
1.10 Product of Symmetry Operations of a Group and the Group Theoretical Rules 21
1.11 Group Multiplication Table 22
1.12 Classification of Elements of a Group 27
Exercises 28

2. Group Representation and Character Table 30–60

2.1 Introduction 30
2.2 Matrices 30
2.2.1 Matrix Multiplication 31
2.2.2 Block-factored Matrices and Column Matrices 32
vii
viii ® Contents

2.2.3 Character of a Matrix 32

2.2.4 Representation of Simultaneous Equation as Matrix Product 33
2.3 Matrix Notation for Symmetry Operation 33
2.4 Group Representation 36
2.5 Character Table 41
2.5.1 The Great Orthogonality Theorem 43
2.5.2 Rules Derived from the Great Orthogonally Theorem 44
2.5.3 Construction of Character Tables 46
2.6 Reducible Representations and Their Reduction 55
2.7 Direct Product 57
Exercises 59

Part II Applications of Group Theory

3. Hybridization of Atomic Orbitals 63–76
3.1 Introduction 61
3.2 Hybridization Scheme in Sigma Bonding 61
3.3 Hybridization Scheme in p-bonding 71
Exercises 76

4. Spectroscopy 77–95
4.1 Introduction 77
4.2 Calculation of Total Character 78
4.3 Identification of IR Active Vibrations 83
4.4 Identification of Raman Active Vibrations 86
4.5 Infrared and Raman Spectra of N2F2 Molecule 87
4.6 Infrared and Raman Spectra of BF3 Molecule 88
4.7 Infrared and Raman Spectra of AB4 Type Molecules 89
4.7.1 Tetrahedral AB4 Molecule 89
4.7.2 Square Planar AB4 Molecule 90
4.7.3 Square Pyramidal AB4 Molecule 90
4.7.4 See-Saw Shaped AB4 Molecule 91
4.8 Octahedral Molecule AB6 92
4.9 Electronic Spectra 92
Exercises 95

5. Molecular Orbital Theory 96–132

5.1 Introduction 96
5.2 LCAO Method 96
5.3 Projection Operator 98
5.3.1 Setting up of Molecular Orbitals 99
5.3.2 Molecular Orbitals of Cyclopropenyl Cation 100
5.3.3 Energy of the C3H+3 Molecular Orbitals 104
5.4 SALC Molecular Orbitals of Benzene 100
5.4.1 Energies of p-Molecular Orbitals of Benzene 109
 Contents ® ix

5.4.2 Shapes of SALC-MOs of Benzene 113

5.4.3 Properties of p-Molecular Orbitals of Cyclic Polyenes 114
5.5 p-Molecular Orbitals of 1,3-Butadiene 114
5.5.1 SALC-MOs of 1,3-Butadiene and Calculation of their Energies 115
5.5.2 Shapes of p-Molecular Orbitals of 1,3-Butadiene 119
5.6 Molecular Orbitals for Regular Octahedral Molecules 120
5.6.1 Formation of SALCs 121
5.7 Tetrahedral AB4 Molecule 123
5.8 Metal Sandwich Compounds 125
5.8.1 Eclipsed Form of Ferrocene 125
5.8.2 Staggered Form of Ferrocene 128
5.8.3 MO Diagram 130
5.9 Dibenzene Chromium 130
Exercises 132
6. Transition Metal Complexes 133–177
6.1 Term Symbols 133
6.2 Ligand Field Theory 138
6.3 Molecular Orbital Theory 144
6.3.1 Octahedral Complexes with p-bonding 148
6.3.2 Tetrahedral Complexes 150
6.4 Splitting of Terms 152
6.5 Correlation Diagrams 153
6.5.1 Method of Descending Symmetry 158
6.5.2 Group-sub-group Relationships 160
6.5.3 Effect of Descent in Octahedral Symmetry on Degeneracy 162
6.5.4 Jahn-Teller Distortion 163
6.6 Electronic Spectra of Transition Metal Complexes 165
6.6.1 Selection Rules 166
6.6.2 Orgel Diagrams 167
6.6.3 Group-sub-group Relationships and Electronic Spectra of
Complexes 170
6.6.4 Tanabe-Sugano Diagrams 172
6.6.5 Influence of Coordination on the Infrared Spectra of Oxoanionic
Ligands 173
Exercises 176
7. Crystal Symmetry 178–193
7.1 Introduction 178
7.2 Symmetry Elements and Operations 178
7.2.1 Proper Rotation Axis 178
7.2.2 Mirror Plane 180
7.2.3 Rotary Inversion Axis 180
7.3 The Crystal Systems 181
x ® Contents

7.4 The 32 Crystallographic Point Groups 181

7.4.1 Stereographic Projections 183
7.5 Bravais Lattices 186
7.6 Translational Symmetry 189
7.6.1 Screw Axis 189
7.6.2 Glide Planes 190
7.7 Space Groups 190
7.7.1 Nomenclature of Space Groups 191
Exercises 193
8. Woodward–Hoffmann Rules 194–201
8.1 Introduction 194
8.2 Application of Woodward–Hoffmann Rules 195
Exercises 201
Appendix A Character Tables for Chemically Important Symmetry Groups 203–214
Appendix B Correlation Table for Group Oh 215
Appendix C Stereographic Projections for the 32 Crystallographic Point Groups 216–217
Index 219–222
 Preface

We are happy to know that there was a good acceptance of the first edition of the book among
the students and teachers of various universities.
Because of the growing importance of the subject, we have decided to revise the contents of
the book by incorporating additional relevant materials. From our teaching experience, we feel
that the units Molecular Orbital Theory and Transition Metal Complexes deserve expansion.
Detailed calculations of benzene and butadiene are, therefore, included in the unit Molecular Orbital
Theory. The slightly higher level of mathematics used in this unit is unavoidable. New topics have
been added to the unit Transition Metal Complexes, namely, group-sub-group relationships, effect
of descent in octahedral symmetry on degeneracy, Jahn-Teller distortion and group-sub-group
relations and electronic spectra of complexes. These topics will also be of great use to the researchers
in the field of coordination chemistry.
Another key feature of the revised edition is the detailed presentation of the topic direct product,
which finds its application in problems related to bonding and spectroscopy in the second unit.
With more examples, the section on space group in Crystal Symmetry has been revised.
We would like to acknowledge Ms. Sangeetha S. and Mr. Ahamed Binu for the help they
have extended for drawing the figures. We express our sincere gratitude to the editorial and
production teams of PHI Learning for the excellent layout and timely publication of this edition
of the book.
We hope that the academic community will extend the same acceptance to this edition also.
We welcome constructive suggestions and criticism.

A. Salahuddin Kunju
G. Krishnan

xi
 Group Theory And Its Applications In
Chemistry

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Author : KUNJU, A.
Publisher : PHI Learning ISBN : 9788120351349 SALAHUDDIN ,
KRISHNAN, G.

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