Journal of Electron Spectroscopy and Related Phenomena, 9 (1976) 334-335 @ Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

Chemistry, Edited by A. D. Butterworths, London, 1975,

Book review

Physical Chemistry, Series Two, Vol. 1: Theoretical Buckingham, F. R. S., and C. A. Coulson, F. R. S., 396 pages, price U.S. $13.45.

This book is the first of thirteen volumes covering Physical and Theoretical Chemistry, Chemical Crystallography and Analytical Chemistry. The late Professor C. A. Coulson was originally the sole editor of the book. In recognition of his contri- butions in the field, the first 26 pages give a complete listing of his publications. The following ten chapters (thirteen authors) deal with some of the recent developments in theoretical chemistry. The major thrust is the treatment of new or standard methods of calculating wave functions and energies of molecules.

The chapter by W. G. Richards and T. E. H. Walker briefly summarizes the Hartree-Fock method and, in particular, the special techniques employed for poly- atomic systems. It also gives a critical survey of which properties of molecules can or have been calculated with the Hartree-Fock method.

The paper by P. Weinberger and K. Schwarz introduces the SCF-Xa-scattered wave method which has, by now, been widely used for the calculation of electronic states in large moIecules and atomic clusters. The treatment of the basic formalisms and concepts is rather detailed, including discussions of the exchange approximation and the transition state. The survey of applications given is necessarily incomplete, as the area has expanded considerably since the writing.

The review on correlated wave functions by N. C. Handy discusses the present state in the determination of high accuracy wave functions for small molecules using either variational methods or the method of moments. After a short introduc- tion into the methods, the examples He, Li, Be and H2 are discussed in detail.

The article on configuration-space Green’s functions by S. M. Blinder gives a basic introduction into the theory of Green’s functions. Here, one might have wished for more detaiIed information on applications or possible applications of the methods in quantum chemistry which are dealt with in only two of forty pages.

The paper by R. F. W. Bader treats a field which has become rather important in the interpretation of results from molecular calculations, the display and use of molecular charge distributions. After a comparison of molecular charge distributions calculated with different methods (near Hartree-Fock, SCF, CI) and some comments on the experimental determination of charge densities, a very detailed discussion, with many examples, on the use of charge difference (bond) densities and, particularIy on the methods of partitioning molecular charge distributions, is given.

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The review on electron momentum distributions in atoms, molecules and solids by I. R. Epstein presents a brief survey on the experimental methods (x-ray, y-ray Compton scattering, high-energy electron scattering, etc.) and then discusses the theoretical concepts and the interpretation of momentum distributions clearly and in detail.

The paper on the theory of rotationally inelastic molecular collisions by G. G. Balint-Kurti gives a comprehensive description of Atom-rigid rotor diatomic molecule collisions before discussing the different approximate methods to compute the inelastic cross sections.

The article, by R. P. Messmer, on chemical bonding aspects of some solid- state phenomena, reviews recent work which has been carried out at the border line of chemical and solid-state physics. It treats bonding in crystalline solids (including quasi one dimensional molecular solids like TTF-TCNQ or Krogmann salt) and in amor- phous solids. In addition, recent developments in the theory of defects and impuritiesare discussed. Here, emphasis is put on large cluster model calculations using standard molecular techniques like EHT or the already-mentioned SCF-Xo( SW method.

The review on ESCA by M. E. Schwartz is restricted to the core electron energy shift aspects of ESCA. After reporting some of the earlier semi-empirical theories, e.g., charge potential models, quantum mechanical models are discussed in detail. Here the author concentrates on ab initio SCF calculations to show the influence of electronic relaxation and the chemical environment on the core electron energy shifts. Finally, some so-called intermediate-level semi-empirical models where ab initio SCF calculations are replaced by semi-empirical techniques like EHT or CNDO are presented. Since this article was finished, much theoretical work has been done in the area of shake-up and shake-off intensities. This area is not covered at all. Therefore, the collection of references (which is said to be complete until 1973) does not correspond to the latest state-of-the-art.

Last, a review on radiationless transitions by J. Jortner and S. Mukamel discusses the theoretical aspects of the interplay between various radiative and nonradiative decays in electronically-excited states of polyatomic molecules.

On the whole, this book gives a fine collection of well-written articles on recent developments in the field of theoretical chemistry. The vast number of references to the original literature and other review articles, together with a good subject index, support this impression. Although some of the chapters do not seem to represent the very latest state-of-the-art, I can recommend the book to those active in the field as well as to scientists who are interested in modern developments in theoretical chemistry.

Klaus Hermann Inst. F. Theor. Physik B; TU Cluusthal ( W. Germany)