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Book Review Solids and Surfaces A Chemist's View of Bonding in Extended Structures. By R. Hoffmann

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Book Reviews are written by invitation from the
editor. Suggestions for books to be reviewed and
for book reviewers are welcome. Publishers should
send brochures or (better) books to the following
address: Redaktion Angewandte Chemie, Postfach 10 11 61, D-6940 Weinheim, Federal Republic
of Germany. The editor reserves the right of selecting which books will be reviewed. Uninvited books
not chosen for review will not be returned.
Solids and Surfaces: A Chemist’s View of Bonding in
Extended Structures. By R . Hoffmann. VCH Publishers,
New York/VCH Verlagsgesellschaft, Weinheim 1988. x,
142 pp., hard cover, $24.95.-ISBN 0-89573-709-4/
Extended structures have become increasingly fashionable
for study in the last two decades. Much progress has occurred towards determining and understanding chemical
and physical properties of compounds of this type, whether
they be solids, surfaces, or macromolecules. Theoretical
models of electronic structure in such systems have also developed beyond the treatment of small molecules or small
unit cells. Most recently, theoretical aspects of solid state
chemistry have moved beyond the purely conceptual, e.g., as
in the Zintl-Klemm rules, towards more quantitative descriptions, which have been around in solid state physics for
some decades. “Solids and Surfaces: A Chemist’s View of
Bonding in Extended Structures” by Roald Hoffmann is an
effective attempt to translate the language of band theory for
chemists. True to his style over the years, his descriptions are
highly pictorial and intuitive - an extremely useful complement to the mathematical formulation in the physics literature. Given this, one can contend that this book also teaches
physicists the particular point of view of chemists for looking
at such problems.
The book begins by setting up the vocabulary of band
theory, i.e., Bloch functions, k-space, etc., in order to develop the ideas behind the construction of energy band diagrams. Such dispersion curves have no analog in molecular
orbital theory, and so “to retrieve a local, chemical, or frontier orbital language in the solid state,” Prof. Hoffmann introduces the connection between density-of-states diagrams
(DOS) and molecular orbital energy level schemes - something which “chemists can sketch ..., intuitively.” Local descriptions fall naturally by partitioning the DOS into various
components, either via atomic orbital or bond orbital contributions. COOP (crystal orbital overlap population) diagrams provide another interpretative tool that gives “a way
to find bonds in the bands that a fully delocalized calculation
gives.” In the remainder of the book, he develops and extends these ideas using numerous examples studied in his
research group over the last several years, e.g., ThCr,Si,,
Chevrel phases, the NiAs -+ MnP transition, as well as surface structural problems involving Ni(l00) with CO, and
various transition metals with the methyl group. Within
these examples, Prof. Hoffmann introduces the ideas of
Peierls distortions, frontier orbital approaches, and the significance of the Fermi level, including its influence over surface reactions.
Verlagsgesellschafi mbH, 0-6940 Weinheim. 1989
As mentioned in the preface, the material in this monograph has already appeared in two review articles, one in
Angewandte Chemie, the other in Reviews of Modern Physics.
One may therefore question the need for such a book. In
addition, a number of other publications exist that discuss
chemical bonding and electronic structure from both physical and chemical points of view. Yet, “Solids and Surfaces”,
through its numerous examples, combines the ideas of bonding and reactivity in molecules with those of both solids and
surfaces - topics which may be too cumbersome and excessive for even a single review article.
Prof. Hojfmann’s self-assessment of this material is aIso
true - the language of solid state physics is much more extensive than what is presented in his book. Yet, it represents an
excellent first step for students and other chemical researchers who are not well versed in the language of electronic structure in the solid state. It may also be a valuable
companion text to one which provides more quantitative
descriptions for those who are interested in more of the details.
Gordon J. Miller [NB 984 IE]
Max-Planck-Institut fur Festkorperforschung
Stuttgart (FRG)
The Chemistry of Sulphones and Sulphoxides. Series: The
Chemistry of Functional Groups. Edited by S. Patai,
Z . Rappoport and C. Stirling. Wiley, Chichester 1988. xvi,
1210 pp., bound, E 235.00.-ISBN 0-471-91588-2
In the well-known and very useful series “The Chemistry
of Functional Groups”, the first volume of which appeared
25 years ago (also edited by S . Patai), we now have for the
first time a comprehensive account of the chemistry of sulfoxides and sulfones. This not only fills a gap in the series,
but also remedies a more general deficiency, as there is no
recent monograph of comparable scope and standard on
these classes of compounds. Such a publication was long
overdue, as sulfoxides and sulfones have come to occupy an
important and established place in the repertoire of organic
chemistry; this is clearly shown, for example, by Chapters 12
and 16 on sulfinyl carbanions and asymmetric syntheses,
Chapters 13 and 14 on rearrangement reactions, or Chapters 22 and 23 on electrochemical and electron transfer reactions.
The editors have succeeded in engaging eminent experts as
authors for the individual chapters, and in addition they
have, of course, the experience needed to bring the separate
contributions together so as to form a consistent whole. Not
surprisingly, therefore, the result is an excellent book-a
handbook in the true sense, and not merely a collection of
The first six chapters (165 pages altogether) deal with the
theoretical and physical-chemical aspects of sulfoxides and
sulfones, and also with their analysis-a very useful chapter
from a practical standpoint. A separate chapter on the chirality of sulfoxides, a topic of great importance to the preparative chemist, is also included here. Next there are three
substantial chapters dealing in turn with the preparation
of open-chain sulfones ( K . Schank, 68 pp.) and sulfoxides (J. Drabowicz, P . Kielbasinski, and M . Mikolajczyk,
146 pp.), and of the corresponding heterocycles ( U . Zoller,
104 pp.). The latter chapter, in accordance with the author’s
own field of research, includes an especially detailed account
of the unusual three-membered ring systems.
OS70-0833jS9/0808-l070 $02.S0/0
Angew. Chem. Inl. Ed. Engl. 28 (1989) No. 8
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bonding, structure, solids, chemists, book, hoffmann, surface, view, extended, review
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