book reviews Editor: W. F. KIEFFER

College of Woortar

Wooster, Ohio

Physical Chemistry, Second Edition

Gilbert W . Ca&llan, University of Mary- land. Addison-Wesley Publishing Co., Reading, Mass., 1971. xxvi + 866 pp. 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 spectros- oopy, 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 per- tinent for the bulk of this second edi- tion. It should be repeated that the treat- ment of thermodynamics and its applica- tions to chemical systems is excellently done, and the additions described here largely remedy deficiencies of the first edi- tion in quantum physical chemistry. Many of the problem lists have been en- larged and improved.

In place of the rather primitive discus- sion of quantum phenomena found in the first edition are essentially three new chap- ters (20, 21, and 22) giving a. more thor- ough introduction to quantum mechanical principles (Chapter 20), with applications to simple systems (Chapter 21), and a de- tailed discussion of the hydrogen atom (Chapter 22). In Chapter 20 are pre- sented the postulates of quantum me- chanics, operator algebra, calculation of expectation values and eigenvalue prob- lems, 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 degen- eracy and separability, and finally the two- body 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 treat- ment for atoms of more than one electron

is at the level of freshman texts and hardly justifies the detailed effort of the preceding seotions. The level and type of discussion for atoms of more than one electron cer- tainly 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. Unfortu- nately, the methods for extension of the independent particle model wsve funotions to more interesting molecules is not olertrly indicated. The construction and prop- erties of atomic hybrid orbitals are shown without clear indications of how these hy- brid orbitals are to he used in the valence bond or molecular orbital wave funotions. Chapter 24, Fundamentals of Spectros- copy, includes qualitative portions from Chapter 20 of the first edition with the ad- dition of well done discussions of quantum mechanics of time dependent systems lead- ing to the selection rules for electromag- netic absomtion orocesses. The sections on chemical kinetics are virtually un- changed, 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 thermody- namics and its applications. The new ad- ditions in quantum cbemistry are of some- what 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.

JOHN P. CHESICK Havevford College

Haverford, Pa

-Reviewed in this Issue

Cilhprl If'. Cavldlon, Phyrirnl (:hemistry, Serorrd Editio~r . . ,443: i .Ildlon Owhin and 11.11. .Jape, Slmmetry, Orhi~als, and Spcctra . . , A433 .lldlon Owhtn nnll N. 11. .Inre, S~pplement for Svnmrrry, Orbitals,

and Sprrrm. Pnhlemi and A~~swers . . . .4.tX< . l f i ~ h o ~ l Yudkin and Rohzn Offord, .\C.uidebook to Biochemistry , . . A.t%l K. 0. C. Vormon. Princiulcs ~f OrmnicSvntheris . . . A434 J. M. ~itroerald.kditor.'Analvtic~ ~hot&hemistrv and

~hotoc~emical ~nalGsis: "solids, Solutions, rtni Polymers . . . A434 New Volumes in Continuing Ser~es . . .A435

Symmetry, Orbitals, and Spectra

Miltaz Orchin and H . H . Jaffe, both of University of Cincinnati. Wiley-Inter- science, New York, 1971. xiii + 396 pp. Figs. and tables. 23.5 X 15.5 om. $16.50.

Supplement for Symmetry, Orbitals, and Spectra. Problems and Answers

Milton Orchin and H . H . Jaffe, with the help of G. Kuehnlenz and R. Ellis. Wilev-Interscience. New York. 1971. vii 4 220 pp. Figs. and tables.' 23 X 15.5 em. $5.95.

In the preface to their book, the authors state, ". . . I ts use isintended to guide the reader through introductory quantum mechanics and molecular orbital theory, the free-electron method and the ealcula- tion of u l t ra~ole 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 in- frared spectroscopy, non-computer meth- ods for Hiickel moleculm orbital calculs, tions and their applications, and the basic concepts of photochemistry and excited- state chemistry, including the Woodward- Hoffman 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 sym- metry, group theory and its spplications, ultraviolet spectra and infrared spectros- copy, 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 me- chanics is a msthemrtticel theory, it is al- most impossible to develop many basic concepts in an essentidly non-mathemati- cal 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 or- bitals and banding in transition-metal complexes, the electronic spectra of in- organic complexes and ions, intensities and selection rules for electronic absorption mectra, etc., are quite readable. Sym- metry, p ~ i n t ' ~ r o u ~ ~ , character table, and the Hiickel moleculsr orbital, etc., are dis- cussed in some detail and the presentations are excellent.

The present book can be used as an in- troductory theoretical chemistry text far . nan-physical chemistry graduate students (i.e., inorganic, organic, or biochemical). I t is also a useful self-studv book for re- neareh rlwmisri who find it dtffirdt lo wad tlrr current litersrurr in trrms of avrumtbd

(Continued m page A4S4)

Volume 49, Number 8, August 1972 / A433