CHEMICAL APPLICATIONS OF GROUP THEORY F. Albert Cotton Department of Chemistry, Texas A&M University College Station, Texas THIRD EDITIONPREFACE The aim, philosophy, and methodology of this edition are the same as they were in earlier editions, and much of the content remains the same. However, there are changes and additions to warrant the publication of a new edition. The most obvious change is the addition of Chapter 11, which deals with the symmetry properties of extended arrays—that is, crystals. My approach may not (or it may) please crystallographic purists; I did not have them in ‘mind as [ wrote it. [had in mind several generations of students I have taught to use crystallography as a chemist’s tool. [ have tried to focus on some of the bedrock fundamentals that I have so often noticed are not understood even by students who have learned to “do a crystal structure.” Several of the chapters in Part I have been reworked in places and new exercises and illustrations added. I have tried especially to make projection operators seem a bit more “user-friendly.” In Part II, besides adding Chapter 11, I have considerably changed Chapter 8 to place more emphasis on LCAO molecular orbitals and somewhat less on hybridization. A section on the basis for electron counting rules for clusters has also been added. Finally, in response to the entreaties of many users, I have written an Answer Book for all of the exercises. This actually gives not only the “bottom line” in each case, but an explanation of how to get these in many cases. The Answer Book will be available from the author at a nominal cost. Tam indebted to Bruce Bursten, Richard Adams, and Larry Falvello for helpful comments on several sections and to Mrs. Irene Casimiro for her excellent assistance in preparing the manuscript. F. Avgert CoTTon College Station, Texas December 1989PREFACE TO THE SECOND EDITION In the seven years since the first edition of Chemical Applications of Group Theory was written, I have continued to teach a course along the lines of this book every other year. Steady, evolutionary change in the course finally led to a situation where the book and the course itself were no longer as closely related as they should be. I have, therefore, revised and augmented the book. The new book has not lost the character or flavor of the old one—at least, T hope not. It aims to teach the use of symmetry arguments to the typical experimental chemist in a way that he will find meaningful and useful. At the same time 1 have tried to avoid that excessive and unnecessary superficiality (an unfortunate consequence of a misguided desire, evident in many books and articles on “theory for the chemist,” to shelter the poor chemist from the rigors of mathematics) which only leads, in the end, to incompetence and its attendant frustrations. Too brief or too superficial a tuition in the use of symmetry arguments is a waste of whatever time is devoted to it. I think that the subject needs and merits a student’s attention for the equivalent of a one- semester course. The student who masters this book will know what he is doing, why he is doing it, and how to do it. The range of subject matter is that which, in my judgment, the great majority of organic, inorganic, and physical chemists are likely to encounter in their daily research activity. This book differs from its ancestor in three ways. First, the amount of illustrative and exercise material has been enormously increased. Since the demand for a teaching textbook in this field far exceeds what I had previously anticipated, I have tried now to equip the new edition with the pedagogic paraphernalia appropriate to meet this need. Second, the treatment of certain subjects has been changed—improved, I hope—as a result of my continuing classroom experience. These improve- vil