MAGNETIC RESONANCE IN CHEMISTRY, VOL. 33, 698-699 (1995)

Book Review

N. M. ATHERTON

Principles of Electron Spin Resonance

Ellis Horwood and PTR Prentice Hall, Physical Chemistry Series, Ellis Horwood, Chichester (1993). pp. 585, $127. ISBN 0 13 721762 5.

In 1973, Atherton published a book en- titled ‘Electron Spin Resonance: Theory and Applications’, which was well re- ceived by the ESR Community. His new book, reviewed here, is dedicated to the same topic. Since 1973 the field of ESR has developed and changed dramat- ically, and new directions (e.g. ENDOR, TRIPLE, ESEEM, HYSCORE, ...) are growing rapidly.

The book consists of 12 chapters. The first, ‘The resonance phenomenon’, gives a short description of ESR up to quan- tum mechanics, spin relaxation and multiple resonances. In the following six chapters, time-averaged phenomena are discussed. Chapter 2 gives an overview of ‘Magnetic interactions and the spin- Hamiltonian’. Chapters 3-7 describe in detail the individual interactions: ‘Iso- tropic hyperfine interactions’ (Chapter 3), ‘The g tensor’ (Chapter 4), ‘Aniso- tropic hyperfine interactions’ (Chapter 5) , ‘High-spin systems’ (Chapter 6) and ‘Quadrupole interaction’ (Chapter 7). The title, not the contents of Chapter 6, however, may be a small problem for those working in the field of coordi- nation chemistry.

An interesting and uncommon (up to now) feature of the treatment of the time-independent spectral parameters is that the discussion of cw-ENDOR tran- sition frequencies is integrated with that of ESR transition frequencies. Didacti- cally this is new, but appears to be well arranged in illustrating the advantages of ENDOR with respect to the actual problems discussed in the individual chapters.

In the second half of the book (Chapters 8-12), the time-dependent phenomena are described. Chapter 8 starts with the basic theory of spin relaxation using a consistent density matrix formalism and arrives at a gener- al expression for the lineshape. In Chap- ter 9, a wide range of contributions to the linewidths in solution ESR spectra are discussed, including the fluctuations in the interactions brought about by chemical or physico-chemical processes (chemical exchange, intermolecular ex- change, Heisenberg exchange). Spin- lattice relaxation, transition

@ 1995 by John Wiley & Sons, Ltd.

probabilities and saturation in multi- level systems are analysed and used for the treatment of ENDOR, ELDOR (electron-electron double resonance), sa- turation transfer ESR and electron- nuclear-nuclear TRIPLE resonance techniques in Chapter 10. In the next chapter, time domain ESR is described. Beginning with pulses and spin echoes, this chapter contains all actual pulse techniques going from electron spin- echo envelope modulation (ESEEM) and pulsed ENDOR to two-dimensional experiments. The last chapter, ‘Time- resolved ESR : spin polarization’, gives a detailed description of CIDEP (chemically induced dynamic electron polarization) and its application. This chapter is followed by ten Appendices which contain some basic theoretical and mathematical tools.

Summing up, one can state that Ather- ton’s new book is far from a repacking of the material of his first book. It is a completely rewritten version and has been totally updated. All new develop- ments are discussed in detail. The theo- retical background is excellently and comprehensively presented, and all this in less than 600 pages. The readers need a graduate-level knowledge of mathe- matics, quantum mechanics and spec- troscopy. I am sure that this book will be well received by all ESR colleagues and those who wish to learn about these techniques. In this respect not only graduate students and postgraduate re- searchers in chemistry and physics, but also those in certain biological fields will be well served.

REINHARD KIRMSE Leipzig Germany

WERNER KUTZELNIGG Einfiihrung in die Theoretische Chemie. Band 1 : Quantenmechanische Grundlagen. Korrigierter Nachdruck VCH, Weinheim (1992). xxiv + 297 pp. DM78. ISBN 3 527 28426 5

Band 2: Die chemische Bindung. Zweite, erganzte und aktualisierte Auflage VCH, Weinheim (1994). xxxiv + 602 pp. DM118. ISBN 3 527 29210 1

The first volume presents a standard introduction to quantum mechanics and its application to atoms. The second volume covers the application of quan- tum chemistry to the diverse pheno- mena of chemical bonding. It starts with a short synopsis of the history of con-

cepts of chemical bonding, and treats the Born-Oppenheimer approximation and the bonding in H2+ and H, along classical lines. On the basis of the molec- ular orbital approach and corrections to the independent particle model (electron correlation), semi-empirical models and their limitations are derived. The au- thor spends much effort in imparting his deep understanding of the physical origin and mechanism of chemical bonding to the reader with detailed though clear arguments. Polar bonds, two- and poly-centre bonding, electron- deficient bonds and hypervaiency are thoroughly explained, often using the in- telligible Huckel model. Special chapters are devoted to x-systems, to transition metal compounds and to intermolecular interactions.

The strength of the this book is the elucidation of the relationships between different models and concepts and between theoretical models and chemi- cal facts. Many aspects are more cor- rectly presented than in some other books, such as Koopmans’ theorem, hybridization and d-participation and localized and delocalized bonds.

While much progress has been achieved during the last two decades in many branches of computational chem- istry, less spectacular advances have oc- cured in recent times in the field of understanding the chemical bonds of stable molecules. Since this book is re- stricted to the latter topic, it was sufi- cient to supplement the 1978 edition by short paragraphs at the end of several chapters and by including some original references. The basic achievements of computational ab initio quantum chem- istry of molecules since 1993 are sum- marized in a new Appendix of 10 pages.

The volume may be recommended to readers who want to achieve a well founded, clear and correct understand- ing of chemical bonding in molecules, and who do not have access to the first edition.

W. H. E. SCHWARZ Siegen, Germany

L. D. QUIN and J. G. VERKAGE (Eds)

Phosphorus-31 NMR Spectral Properties in Compound Characterization and Structural Analysis

VCH Weinheim, New York, 1994, xv + 455

3’P NMR has been so thoroughly inte- grated into the spectroscopic armament

pp. DM 260.-, f104.00, ISBN 1 56081 637 6.