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Book Review Molecular Structure and Energetics. Edited by J. F. Liebman and A. Greenberg

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study adsorbed molecules, particularly with regard to their
orientations. Since this effect depends on the strength of
the local electromagnetic field at the surface, it can be used
to measure the field, a capability which is important for
the SERS effect discussed in the next paper.
Surface-enhanced Raman spectroscopy (SERS) has already been reviewed in numerous articles. D . A. Weitz, M .
Moskovits, and J . A. Creighton, in their article “SurfaceEnhanced Raman Spectroscopy with Emphasis on LiquidSolid Interfaces” (51 pp.), support the view that the only
significant factor in the SERS effect is the amplification of
the electromagnetic field by resonance phenomena in
small particles or at rough surfaces, which is highly controversial. There are many indications that a considerable
contribution to the very high enhancement factors of lo5I O6 arises from specific chemical interactions between the
adsorbate and the substrate. The SERS effect is of importance in its application to investigating problems of practical interest, some of which are briefly discussed here. An
example is adsorption on small catalyst particles.
The luminescence observed from semiconductors, either
following excitation by absorption of light or as a result of
the injection of minority carriers, comes from the bulk material. However, its intensity is surface-dependent, since
the radiation yield is determined essentially by the amount
of radiationless recombination occurring at the surface. In
his contribution “Luminescent Properties of Semiconductor Electrodes” (100 pp.), A. B. Ellis describes the experimental requirements for observing the phenomena that occur at semiconductor electrodes, and the theoretical models used to analyze the results. The main interest in such
experiments is in evaluating semiconductors for energy
conversion purposes, as the yield in photoelectrochemical
cells is limited essentially by surface recombination.
All these articles provide interesting and stimulating
ideas on the use of lasers and other optical techniques for
the characterization of interfaces. The techniques that are
proposed are still undergoing development, but undoubtedly have great potential for the future.
Heinz Gerischer [NB 812 IE]
Fritz-Haber- Institut
der Max-Planck-Gesellschaft, Berlin-Dahlem
Molecular Structure and Energetics. Edited by J. F. Liebman and A . Greenberg. VCH Verlagsgesellschaft, Weinheim/VCH Publishers, Deerfield Beach, FL 1986. Vol.
1: Chemical Bonding Models. XIV, 360 pp., bound, DM
240.00 (subscription price DM 210.00).--ISBN 3-52726344-6/0-89573-139-8; Vol. 3: Studies of Organic Molecules. XIV, 385 pp., bound, DM 240.00 (subscription
price DM 2 10.00). -ISBN 3-527-26477-9/0-89573-141-X
A new “open-end” series has been started and the volumes 1 and 3 published first - in the meantime volumes 2
and 4 also appeared - contain 360 und 385 pages respectively; they have been published by the US subsidiary of
VCH Verlagsgesellschaft, our old friend Verlag Chemie, in
the same esthetic way to which we have become accustomed. (The binding is not to my taste but de gustibus not
est disputandum). ,
Each of the two volumes has a general heading and the
contributions chosen fit in reasonably well. Each author
was given much latitude in the relative blending of theory
and experiment and in style. This is perhaps most evident
in the chapters written or co-authored by the editors themAngew. Chem. Int. Ed. Engl. 26 (1987) No. I 1
selves. The standard of the contents, almost without exception, is very high.
In comparing two similar series, published as beautifully
as this one by a competing publisher (“Structure and
Bonding” and “Topics in Current Chemistry”), one finds
similar breadth and homo- or heterogeneity. It is evident
that it is cheaper to print in East or even in West Germany
per individual volume than in the U. S.
Not as a matter of modesty, but as a matter of fact, I
have checked my opinions on chapters further from my realm of understanding with trusted expert colleagues.
Though they remain unidentified, any misjudgements are
solely my responsibility.
Volume 1 contains nine chapters, the first of which (15
pages) is by L. Pauling and 2. S . Herman. What a nice idea
for the opening chapter of a book on chemical bonding!
Although one can always learn from Pauling, 1, of course,
included (albeit Vitamin C is unmentioned), I must abjectly confess my disappointment. I was looking forward
to a much greater treat upon reading the first half of the
title: “Nature of the Chemical Bond Fifty Years Later:” I
expected from the Master a deeper evaluation and perspective than actually touched. The purpose of sub-heading “The Relative Electronegativity of Atoms Seen in Perspective” is achieved. I expected a wider overview on the
nature of the chemical bond, 50 years later, perhaps employing more of “the work of such investigators as Roald
Hoffmann”. Perhaps my judgement is clouded by the nature of the first chapter (by D. J. Cram) in a two-volume
set on cyclophanes.
Chapter 2 by H . A. Bent on “Isoelectronic Molecules”
treats the subject in an incredibly terse manner (30 pages!),
as can be done only by a leading expert; it explains the
concepts involved with well chosen examples. I was sorry
when the beautifully written chapter ended. I should have
been glad to see included the word isolobal.
Chapter 3 by J . F. Liebman and J. Simons discusses
“Carbenes: A Study in Quantitative and Qualitative Theory” (49 pages). Since reviews of carbenes emphasizing the
synthetic viewpoint are plentiful, this one is particularly
In Chapter 4, M . S . Gordon considers “Theoretical Studies of Multiple Bonding to Silicon” (22 pages). The author’s first sentence makes the point of how rapidly this
new field is developing. The length of the chapter is due to
the novelty of the field and though coverage is very good
Si=N bonding might have been added when Si=P is discussed. The author even manages to cite some 1985 references which were available to him, but much has already
appeared in the interim. It is a pity that in this case there is
no addendum (as in Vol. 3) to catch up a bit more. Nevertheless, here is the place to mention that publication has
been relatively fast and many 1984 references are cited
In contradistinction, Chapter 5 by R . B. King on “Topological Relationships in Molecular Structures and Energetics” (26 pages) is disappointing. It not only skims the surface but its latest 1983 reference is to a chapter elsewhere
by the same author on the same general theme. I should
have thought that a chapter with this title ought to have
contained a bit more about graph theory to simple planar
organic compounds if not to those few that cannot be accommodated by a planar graph. Perhaps a more limiting
title could not have led to great expectations.
Chapter 6 by T. P. Fehlner and C. E. Housecroft discusses “Boranes and Heteroboranes” (59 pages). It is a
good introduction to the uninitiated as to structures of
cluster compounds, those of boron being perhaps the most
versatile examples. Other clusters are mentioned in Chapter 5. This is a place where the editors might have had a bit
more substantive inter-connection between the two rather
than just placing them adjacently.
J. K . Burdett writes about “Structural-Electronic Relationships in the Solid State” in Chapter 7 (65 pages). It is
here again unfortunate that other than two (self) citations
from 1985. Nevertheless, this is an excellent review on the
subject with examples from a variegated array of molecules. This chapter is one of the best in the Series.
Chapter 8 by two excellent authors, L. J. Schaad and B.
A . Hess, Jr. on “A Detailed Derivation of the Schrodinger
Equation” (42 pages) is out of place even in a book with
such a broad subtitle, the explanation in its first paragraph
notwithstanding. Nor d o several theoreticians whom I consulted see any justification for its inclusion.
Chapter 9 by J. E. De1 Bene on “Quantum Chemical
Reaction Enthalpies” need not scare away any organic
chemist. Added to the interesting discussion is a very helpful appendix regarding basis set and method notation.
Volume 3 contains seven chapters on almost entirely unrelated subjects. Though heterogeneous we have a collection of interesting discussions, some more specific, some
more general. I have found the latter generally useful but I
predict that readers will rate the more specific subjects in
accord with their interests.
Chapter 1 is a n authoritative review by S. F. Nelsen on
“Hydrazine-Hydrazine Cation Electron Transfer Reactions” (56 pages), a field in which the author is the major
contributor. It is a goldmine of information while explaining relative behavior principally by conformational
Chapter 2 by G. R. Stevenson on “Stabilization and Destabilization of Aromatic and Antiaromatic Compounds”
(27 pages) is to me another in a long chain of books and
chapters still flogging this creature. I say this seriously but
the tongue-in-cheek statement by E. Heilbronner about
“schizoaromaticity” (a compound believes itself aromatic
by one criterion, not so by another) summarizes my feelings about this subject. Annulenes are emphasized and
other than a handful of references to his own more recent
work the citations are mainly from the 60’s and 70’s. I do
not see the need for a chapter such as this.
Chapter 3 by R . P. Johnson on “Structural Limitations
in Cyclic Alkenes, Alkynes, and Cumulenes” (56 pages)
cites a great many from the late 70’s and the 80’s including
some from 1985. Thus it is a useful up-to-date review
nicely blending theory and experiment. I missed explicit
citation of Sondheimer’s classic work. It ought, perhaps, to
have been fitted into the discussion.
Chapter 4 by B. F. Smart on “Fluorinated Organic Molecules” ( 5 l pages). (As an aged conservative I enjoyed the
note explaining how to convert kcal/mol into SI units!
This is dealt with in Chapter 6 in a more kosher manner.)
The review is an excellent addition to another by the same
author (Ref. 2). Troubles with experimental accuracy and
problems in calculations are well illustrated.
Chapter 5 by A . Greenberg and T. A . Stevenson discusses
“Structures and Energies of Substituted Strained Organic
Molecules” (74 pages); it is an expectedly fitting sequel to
the Liebman-Greenberg monograph on the same topic and
a rich source of updated experimental and calculated
Chapter 6 by J . F. Liebman has relatively little to d o
with strain. It is entitled “Macroincrementation Reactions:
A Holistic Estimation Approach for the Properties of Organic Compounds” (62 pages). Graduate students in
chemistry as well as their teachers would d o well to enjoy
the well written story of heats of formation and their correct application, remembering not to compare apples with
pears. They might even learn the meaning of some words
in the title. Here again many recent citations are given. The
use of comments bracketed by the symbol Q % are an original way for emphasis.
Chapter 7 by E. Gsawa and K . Kanematsu discusses
“Generation of Long Carbon-Carbon Single Bonds in
Strained Molecules by Through-Bond Interactions” (41
pages; the 4 % method employed). It is not surprising
that such a fine theoretician-experimentalist team has produced such a valuable chapter. All in all: The Series is a
must for every chemical library.
David Ginsburg [NB 833 IE]
Department of Chemistry
Israel Institute of Technology
Haifa (Israel)
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