Group Theory for Chemists: Fundamental Theory and Applications

standards.

Preface

The book I have written is based on a course of approximately 12 lectures and 6 hours of tutorials and workshops given at the University of Bath. The course deals with the basics of group theory and its application to the analysis of vibrational spectra and molecular orbital theory. As far as possible I have tried to further refer group theory to other themes within inorganic chemistry, such as the links between VSEPR and MO theory, crystal field theory (CFT) and electron deficient molecules. The book is aimed exclusively at an undergraduate group with a highly focussed content and thus topics such as applications to crystallography, electronic spectra etc have been omitted. The book is organised to parallel the sequence in which I present the material in my lectures and is essentially a text book which can be used by students as consolidation. However, group theory can only be mastered and appreciated by problem solving, and I stress the importance of the associated problem classes to my students. Thus, I have interspersed self-assessment questions to reinforce material at key stages in the book and have added additional exercises at the end of most chapters. In this sense, my offering is something of a hybrid of the books by Davidson, Walton and Vincent.

I have made two pragmatic decisions in preparing this book. Firstly, there is no point in writing a textbook that nobody uses and the current vogue among undergraduates is for shorter, more focussed texts that relate to a specific lecture course; longer, more exhaustive texts are likely to remain in the bookshop, ignored by price-conscious purchasers who want the essentials (is it on the exam paper?) and little more. Secondly, the aim of a textbook is to inform and there seems to me little point in giving a heavily mathematical treatment to a generation of students for whom numbers are an instant turn-off. I have thus adopted a qualitative, more pictorial approach to the topic than many of my fellow academics might think reasonable. The book is thus open to the inevitable criticism of being less than rigorous, but, as long as I have not distorted scientific fact to the point of falsehood, I am happy to live with this.

Note for Students

Group theory is a subject that can only be mastered by practising its application. It is not a topic which lends itself to rote-learning, and requires an understanding of the methodology, not just a knowledge of facts. The self-assessment questions (SAQs) which can be found throughout the book are there to test your understanding of the information which immediately precedes them. You are strongly advised to tackle each of these SAQs as they occur and to check your progress by reference to the answers given in Appendix 3. Longer, more complex problems, some with answers, can be found at the end of each chapter and should be used for further consolidation of the techniques.

Note for Lecturers

In addition to the SAQs and problems for which answers have been provided there are a number of questions at the end of most chapters for which solutions have not been given and which may be useful for additional tutorial or assessment work.

Acknowledgements

In producing the lecture course on which this book is based I relied heavily on the textbook Group Theory for Chemists by Davidson, perhaps naturally as that author had taught me the subject in my undergraduate years. Sadly, that book is no longer in print – if it were I would probably not have been tempted to write a book of my own. I would, however, like to acknowledge the influence that book primus inter pares* has had on my approach to teaching the subject.

I would also like to offer sincere thanks to my colleagues at the University of Bath – Mary Mahon, Andy Burrows, Mike Whittlesey, Steve Parker, Paul Raithby – as well as David Cardin from the University of Reading, for their comments, criticisms and general improvement of my original texts. In particular, though, I would like to thank David Liptrot, a Bath undergraduate, for giving me a critical student view of the way the topics have been presented. Any errors and shortcomings that remain are, of course, entirely my responsibility.

Kieran Molloy,     University of Bath, August 2010

*Other texts on chemical group theory, with an emphasis on more recent works, include:

J S Ogden, Introduction to Molecular Symmetry (Oxford Chemistry Primers 97), OUP, 2001.

A Vincent, Molecular Symmetry and Group Theory: A Programmed Introduction to Chemical Applications, 2nd Edition, John Wiley and Sons, 2000.

P H Walton, Beginning Group Theory for Chemistry, OUP, 1998.

M Ladd, Symmetry and Group Theory in Chemistry, Horwood Chemical Science Series, 1998.

R. L. Carter, Molecular Symmetry and Group Theory, Wiley and Sons, 1998.

G Davidson, Group Theory for Chemists, Macmillan Physical Science Series, 1991.

F A Cotton, Chemical Applications of Group Theory, 3rd Edition, John Wiley and Sons, 1990.

Part I

Symmetry and Groups

1

Symmetry

While everyone can appreciate the appearance of symmetry in an object, it is not so obvious how to classify it. The amide (1) is less symmetric than either ammonia or borane, but which of ammonia or borane – both clearly symmetric molecules – is the more symmetric ? In (1) the single N-H bond is clearly unique, but how do the three N-H bonds in ammonia behave ? Individually or as a group ? If as a group, how ? Does the different symmetry of borane mean that the three B-H bonds will behave differently from the three N-H bonds in ammonia ? Intuitively we would say yes, but can these differences be predicted ?

This opening chapter will describe ways in which the symmetry of a molecule can be classified (symmetry elements and symmetry operations) and also to introduce a shorthand notation which embraces all the symmetry inherent in a molecule (a point group symbol).

1.1 SYMMETRY

Imagine rotating an equilateral triangle about an axis running through its midpoint, by 120° (overleaf). The triangle that we now see is different from the original, but unless we label the corners of the triangle so we can follow their movement, it is indistinguishable from the original.

The symmetry inherent in an object allows it to be moved and still leave it looking unchanged. We define such movements as symmetry operations, e.g. a rotation, and each symmetry operation must be performed with respect to a symmetry element, which in this case is the rotation axis through the mid-point of the triangle.

It is these symmetry elements and symmetry operations which we will use to classify the symmetry of a molecule and there are four symmetry element ⁄ operation pairs that need to be recognised.

1.1.1 Rotations and Rotation Axes

In order to bring these ideas of symmetry into the molecular realm, we can replace the triangle by the molecule BF3, which valence-shell electron-pair repulsion theory (VSEPR) correctly predicts has a trigonal planar shape; the fluorine atoms are labelled only so we can track their movement. If we rotate the molecule through 120° about an axis perpendicular to the plane of the molecule and passing through the boron, then, although the fluorine atoms have moved, the resulting molecule is indistinguishable from the original. We could equally rotate through 240°, while a rotation through 360° brings the molecule back to its starting position. Each of these rotations is a symmetry operation and the symmetry element is the rotation axis passing through boron.

Fig. 1.1 Rotation as a symmetry operation.

Remember, all symmetry operations must be carried out with respect to a symmetry element. The symmetry element, in this case the rotation axis, is called a three-fold axis and is given the symbol C3. The three operations, rotating about 120°, 240° or 360°, are given the symbols C3¹, C3² and C3³, respectively. The operations C3¹ and C3² leave the molecule indistinguishable from the original, while only C3³ leaves it identical. These two scenarios are, however, treated equally for identifying symmetry.

In general, an n-fold Cn axis generates n symmetry operations corresponding to rotations through multiples of (360 ⁄ n)°, each of which leaves the resulting molecule indistinguishable from the original. A rotation through m × (360 ⁄ n)° is given the symbol Cnm. Table 1 lists the common rotation axes, along with examples.

Table 1.1

Examples of common rotation axes.

Where more than one rotation axis is present in a molecule, the one of highest order (maximum n) is called the main (or principal) axis. For example, while [C5H5]− also contains five C2 axes (along each C-H bond), the C5 axis is that of highest order. Furthermore, some rotations can be classified in more than one way. In benzene, C6³ is the same as C2¹ about a C2 axis coincident with C6. Similarly, C6² and C6⁴ can be classified as operations C3¹ and C3² performed with respect to a C3 axis also coincident with C6.

The operation Cnn e.g. C2², always represents a rotation of 360° and is the equivalent of doing nothing to the object. This is called the identity operation and is given the symbol E (from the German Einheit meaning unity).

SAQ 1.1: Identify the rotation axes present in the molecule cyclo-C4H4 (assume totally delocalised π-bonds). Which one is the principal axis ?

Answers to all SAQs are given in Appendix 3.

1.1.2 Reflections and Planes of Symmetry

The second important symmetry operation is reflection which takes place with respect to a mirror plane, both of which are given the symbol σ. Mirror planes are usually described with reference to the Cartesian axes x, y, z. For water, the xz plane is a mirror plane :

Fig. 1.2 Reflection as a symmetry operation.

Water has a second mirror plane, σ(yz), with all three atoms lying in the mirror plane. Here, reflection leaves the molecule identical to the original.

Unlike rotation axes, mirror planes have only one associated symmetry operation, as performing two reflections with respect to the same mirror plane is equivalent to doing nothing i.e. the identity operation, E. However, there are three types of mirror plane that need to be distinguished. A horizontal mirror plane σh is one which is perpendicular to the main rotation axis. If the mirror plane contains the main rotation axis it is called a vertical plane and is given the symbol σv. Vertical planes which bisect bond angles (more strictly, one which bisects two σv or two C2 operations) are called dihedral planes and labelled σd, though in practice σv and σd can be treated as being the same when assigning point groups (Section