book reviews

Editor: W. F. KIEFFER
College of Woortar Wooster, Ohio

Symmetry, Orbitals, and Spectra

Miltaz Orchin and H . H . Jaffe, both of University of Cincinnati. Wiley-Inter396 science, New York, 1971. xiii pp. Figs. and tables. 23.5 X 15.5 om. $16.50.

Supplement for Symmetry, Orbitals, and Spectra. Problems and Answers Physical Chemistry, Second Edition

Gilbert W . Ca&llan, University of Maryland. Addison-Wesley Publishing Co., 866 pp. Reading, Mass., 1971. xxvi Figs. and tables. 24.2 X 17 em. $14.95. Exeeot for the addition of three new chapters giving e.smtinlly n w and d c tailed discus9ims uf quxntum mwhnnivs and some applications to simple systems, and revisions and additions to chapters on covalent bonding and molecular spectrosoopy, this text is virtually the same as the first edition. The reader is referred to the first review [J. CHEM. EDUC., 41, 577 (1964)l for comments which remain pertinent for the bulk of this second edition. It should be repeated that the treatment of thermodynamics and its applications to chemical systems is excellently done, and the additions described here largely remedy deficiencies of the first edition in quantum physical chemistry. Many of the problem lists have been enlarged and improved. In place of the rather primitive discussion of quantum phenomena found in the first edition are essentially three new chapters (20, 21, and 22) giving a. more thorough introduction to quantum mechanical principles (Chapter 20), with applications to simple systems (Chapter 21), and a detailed discussion of the hydrogen atom (Chapter 22). In Chapter 20 are presented the postulates of quantum mechanics, operator algebra, calculation of expectation values and eigenvalue problems, perturbation theory, and a proof of the variation principle. In Chapter 21 these methods are applied to the free particle, particle in a box, the uncertainty principle, and the harmonic oscillrttor. The osoillator problem is set up and p a tially solved with a. statement given for the final solution. The three-dimensional box problem is included to illustrate degeneracy and separability, and finally the twobody problem is set up with separation of varisbles and statement of the solution in terms of Legendre polynomials for the rigid rotor. Chapter 22 continues the two-body problem for a, centrd field, namely the hydrogen atom. Unfortunately the treatment for atoms of more than one electron

In the preface to their book, the authors state, ". . . Its use isintended to guide the reader through introductory quantum mechanics and molecular orbital theory, the free-electron method and the ealculation of u l t r a ~ o l e t spectra, symmetry, group theory and its applications, the struoture, bonding, and ultraviolet spectra of inorganic and arganometal complexes, selection rules governing the intensities of absorption bands, the fundamentals of infrared spectroscopy, non-computer methods for Hiickel moleculm orbital calculs, tions and their applications, and the basic concepts of photochemistry and excitedstate chemistry, including the WoodwardHoffman rules for the conversion of orbital symmetry in concerted reactions." In this reviewer's opinion the authors have not entirely succeeded in guiding the reader through introductory quantum mechanics and molecular orbital theory but have done an excellent job on the topics of symmetry, group theory and its spplications, ultraviolet spectra and infrared spectroscopy, snd have done a reasonably good job on the other topics. The descriptive treatments of the first three chapters of the present text hardly provide clear basic concepts of quantum mechanics and moleodar theory. I t may not be adequate to mention the variational principle until the lster part of the book and to omit the discussion of perturbation theory completely, since quantum mechanics is a msthemrtticel theory, it is almost impossible to develop many basic concepts in an essentidly non-mathematical form without misunderstanding. Only some basic knowledges of linear algebra is needed to introduce many important quantum mechanical concepts in a rigorous manner. The chapters on linear- and cross-conjugated molecules, symmetry orbitals and banding in transition-metal complexes, the electronic spectra of inJOHN CHESICK organic complexes and ions, intensities and P. selection rules for electronic absorption Havevford College mectra, etc., are quite readable. SymHaverford, Pa metry, p ~ i n t ' ~ r o character table, and u~~, the Hiickel moleculsr orbital, etc., are dis-Reviewed in this Issue cussed in some detail and the presentations are excellent. ,443:i Cilhprl If'. Cavldlon, Phyrirnl (:hemistry, Serorrd Editio~r The present book can be used as an in. . ,A433 .Ildlon Owhin and 11.11. .Jape, Slmmetry, Orhi~als, Spcctra and troductory theoretical chemistry text far .lldlon Owhtn nnll N.11. .Inre, S~pplement Svnmrrry, Orbitals, for nan-physical chemistry graduate students . ..4.tX< and Sprrrm. Pnhlemi and A ~ ~ s w e r s (i.e., inorganic, organic, or biochemical). , .A l t % . . l f i ~ h o Yudkin and Rohzn Offord, .\C.uidebook to Biochemistry ~l I t is also a useful self-studv book for re.A434 K. 0.C . V o r m o n . Princiulcs ~f OrmnicSvntheris neareh rlwmisri who find it dtffirdt lo wad J . M. ~itroerald.kditor.'Analvtic~ ~hot&hemistrv and tlrr current litersrurr in trrms of avrumtbd . .A434 ~hotoc~emical ~nalGsis: "solids, Solutions, rtni Polymers .A435 New Volumes in Continuing Ser~es
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is at the level of freshman texts and hardly justifies the detailed effortof the preceding seotions. The level and type of discussion for atoms of more than one electron certainly is far below that of the bulk of the text. The discussion of the covalent bond in the first edition has been expanded by a much more detailed discussion of valence bond and molecular orbital functions for Hz+ and HI in Chapter 23. Unfortunately, the methods for extension of the independent particle model wsve funotions to more interesting molecules is not olertrly indicated. The construction and properties of atomic hybrid orbitals are shown without clear indications of how these hybrid orbitals are to he used in the valence bond or molecular orbital wave funotions. Chapter 24, Fundamentals of Spectroscopy, includes qualitative portions from Chapter 20 of the first edition with the addition of well done discussions of quantum mechanics of time dependent systems leading to the selection rules for electromagnetic absomtion orocesses. The sections on chemical kinetics are virtually unchanged, including the discussion of HZ L as a hiomolecular reaction, known now to be incorrect. There has been added a brief section on relaxation methods in chemical kinetics. In summary, of the top level physical chemistry texts which attempt to cover essentially all of the principal areas of physical chemistry in one volume; this is in the reviewer's opinion by far the best and most carefully done text for thermodynamics and its applications. The new additions in quantum cbemistry are of somewhat uneven depth and utility, but there is more than enough to fill available time in s yem survey course. The chemical kinetics portions of the text are generally satisfactory, if undistinguished. The choice of this text or one of its competitors, e.g., Moore's or that of Eggers, Gregory, Halsey, and Rabinovitch, is likely to hinge on the relative emphssis of topics in the course.

Milton Orchin and H . H . Jaffe, with the help of G. Kuehnlenz and R. Ellis. Wilev-Interscience. New York. 1971. 220 pp. Figs. and tables.' 23 X vii 15.5 em. $5.95.

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Volume 49, Number 8 , August 1972

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