[Review] Deciphering the Chemical Code: Bonding Across the Periodic Table Page: 7,908

                                
7908 J. Am. Chem. Soc., Vol. 119, No. 33, 1997
discusses nitrocarbons that might exist and related highly nitrated
compounds. With the exception of TNM, the principal interest in these
materials is for use in explosive and propellant formulations. TNM
has also found use as a nitration reagent and as a polymerization
catalyst.
Nielsen is the right person to author this book. He had co-authored
an earlier book in the Organic Nitro Chemistry series and until his
retirement from the Navy lab at China Lake, was one of the premier
chemists in energetic materials.
For those interested in the subject, this is an invaluable source
compiling data from over 1000 references, many of which are hard to
find Russian publications.
Jimmie C. Oxley, University of Rhode Island
JA955348M
S0002-7863(95)05348-0
Total Reflection  X-Ray   Fluorescence  Analysis.  Chemical
Analysis, Vol. 140. By Reinhold Klockenkamper (Institut fur
Spektrochemie   und    Angewandte    Spektroskopie-Dortmund,
Germany). John Wiley: New     York.  1997. xvii +   245 pp.
$69.95. ISBN 0-471-30524-3.
Most chemists know that the basis of classical X-ray fluorescence
(XRF) spectroscopy is the fact that a suitably-excited atom exhibits a
characteristic X-ray spectrum. Total reflection (T) of X-rays (which
occurs when the glancing angle of the incident beam is less than a
critical angle) was first discovered by Compton in 1923, but was not
applied to XRF until the early 1970s. Over the past 20 years,
concomitant with the advances in solid-state detector sensitivity and
X-ray source intensity, TXRF has been developed into an important
analytical tool. The low sample detection limit (10-12 g), the minimal
surface penetration of the incident beam (1-500 nm), and the near
elimination of spectral background and matrix effects combine to make
this a recommended method for both microquantitative analysis and
surface analysis. However, TXRF differs fundamentally from classical
XRF since the totally reflected X-ray beam (glancing angle <0.1)
interferes with the incident primary beam to form standing waves above
the sample surface and within near-surface layers. Consequently, the
instrumentation requirements and data analysis methodology are unique
to TXRF and are not simply extensions of classical XRF methods.
Currently, in atomic spectroscopy TXRF competes with instrumental
neutron activation analysis (INAA), while in surface and thin-layer
studies it compares favorably with Rutherford back-scattering (RBS)
and secondary ion mass spectrometry (SIMS).
This volume, written by a well-known expert in the field, is the
first book solely dedicated to TXRF. It is clearly written with excellent
coverage of theory, instrumentation, sample preparation, data collection
and interpretation, and a wide range of applications (chemical analysis,
environmental studies, medicine, industrial materials, and forensics).
The book closes with a discussion of future prospects in this exciting
and developing field.
Total Reflection X-Ray Fluorescence Analysis, which contains
introductory background material along with detailed practical experi-
mental hints, is an excellent survey of the current status of TXRF for
both specialists and nonspecialists (including instructors of analytical
chemistry). The bibliography is thoroughly representative and reason-
ably current; in future years it can be kept up-to-date by reference to
the biennial reviews of X-ray spectroscopy which appear in Analytical
Chemistry (e.g., 1996, 68, 467R).
Reuben Rudman, Adelphi University
JA975500F
S0002-7863(97)05500-5

Book Reviews

Deciphering the Chemical Code: Bonding Across the Periodic
Table. By Nicolaos D. Epiotis (University of Washington). VCH:
New York. 1996. xlvii + 933 pp. $89.95. ISBN 1-56081-946-4.
This work describes a new theoretical framework for describing
chemical bonding. A prime motivation is to overcome shortcomings
in "popular" theories used to explain chemical phenomena. To do so
requires a blizzard of abbreviations unlike anything this reviewer has
seen since the section of my college history textbook covering the New
Deal. To some extent, this problem is unavoidable given the focus of
the work. The author includes a pictorial glossary of new terms at the
beginning of the book to help deal with this daunting "alphabet soup",
an excellent idea and one authors of related monographs would do well
to consider.
The book is, at over 900 pages, not a "quick read". In places the
reading is slow going although this is expected since many concepts
are unlike those employed in bonding theories familiar to chemists. In
other areas the writing is in a style one could almost classify as
colloquial; you get the impression the author is speaking directly to
you, attempting to convince you of his arguments. There are also many
intriguing chapter titles including The Skeleton in the Closet of
Inorganic Chemistry, How Theoretical Inorganic Chemistry Went
Astray, and Computational Chemistry: Curse or Panacea? to pique the
curiosity.
The central thesis behind much of this book is that previous attempts
at codifying electronic structure theory fail to focus on an important
chemical concept, i.e., the importance of electron-electron repulsion.
If one considers the simple orbital-driven arguments typically used to
explain observations (e.g., the preference for one isomer over another,
the stereo- and regiochemistry of a reaction, etc.) then there is much
to support the hypothesis that modem electronic structure theory focuses
primarily on the one-electron portion of the energy to the neglect of
the two-electron portion. Given this, any work that seeks to expand
this view is valuable.
Another primary goal of this work is, as the title suggests, to develop
a theoretical framework that is applicable across the entire periodic
table as opposed to developing specific theories for specific families
of elements. Fundamental problems in the electronic structure of
organic, main group, and transition metal compounds are treated.
Perhaps more importantly, the emphasis is on developing qualitative
(and semiquantitative) concepts that can be used not only to rationalize
the results of experiments and high-level calculations but also as a tool
for predicting new chemistry.
Another central thesis of this work is that despite recent advances
in computational chemistry many of the fundamental theories used to
rationalize numerical results are those developed many years ago by
Lewis, Pauling, etc. Epiotis develops new concepts such as the
interstitial and exchange bond. Will it revolutionize our ways of
thinking about bonding in chemistry? The pessimistic view suggests
that such an effort will fail given the chemist's inertia toward new
bonding models. On the other hand, concepts are couched in the
language of valence bond theory, which, despite the fact that the
overwhelming majority of computational chemistry studies reported
in journals such as this employ the molecular orbital formalism, is near
and dear to the hearts of chemists, experimentalists, and theorists alike.
In summary, this book may be of interest to anyone with an interest in
theories of chemical valence.
Thomas R. Cundari, University of Memphis
JA965712X
S0002-7863(96)05712-5