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Electron Spin Resonance. Analysis and Interpretation. By PhilipH. Rieger

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Angewandte
Books
Chemie
Electron Spin Resonance
Analysis and Interpretation. By Philip H. Rieger. Royal
Society of Chemistry, Cambridge
2007. 274 pp.,
hardcover
£ 79.95.—ISBN
978-0-85404-355-1
Electron paramagnetic resonance (EPR)
or electron spin resonance (ESR)
spectroscopy is the most informative
method for elucidating electronic structure of compounds with unpaired electrons. Such compounds are usually highly
reactive or catalytically active, and consequently they are encountered in many
important chemical processes as well as
in living organisms. Therefore, EPR
spectroscopy is typically applied in catalyst research, in the characterization of
metalloproteins and radical enzymes,
and in studies of the degenerative processes induced by free radicals in living
cells. The main current developments in
EPR methods are a widening of the
scope of pulse techniques, measurements
at high fields and frequencies, and an
extension of the set of techniques that
are applicable to site-directed spinlabeled biomacromolecules.
This book cannot be assigned to any
of these new trends, but it is a very
welcome addition to the literature in the
field of EPR spectroscopy. This is
because the required basis of even the
most advanced methods and applications still is, and will continue to be, a
solid understanding and correct interpretation of continuous-wave (CW)
Angew. Chem. Int. Ed. 2008, 47, 2913 – 2914
EPR spectra. This is the topic of the
book, and its approach is fresh and
didactically sound.
The main strength of this approach
lies in the wisdom of limiting the discussion to those questions that arise in
measuring and interpreting spectra. The
physical fundamentals are treated only to
the extent that is required for understanding practical problems. Thus, the
book is accessible to a broader readership
than existing textbooks, which are geared
to the interests of EPR spectroscopists
who work on method development.
This concept of the author is already
well illustrated in the introductory chapter. The spin Hamiltonian and technical
aspects of the measurement are treated
on just a few pages, yet at a level that is
sufficient to understand the following
considerations about optimizing the
acquisition of spectra. This short but
complete and easily understandable
explanation of measurement parameters surpasses any previous treatment
that I have read (or written myself).
The next chapters introduce, step by
step, complications that arise in spectra
through the coupling of electron spins to
several nuclear spins in an isotropic
solution, through incomplete averaging
of anisotropic interactions, and through
the orientation dependence of parameters in the solid state. In a very intuitive
way, theoretical concepts are explained
by analyzing example spectra. The complexity of these spectra increases gradually. After showing how such spectra
are reduced to the parameters of the
spin Hamiltonian, the author explains
how these parameters are related to
electronic structure, again using illustrative examples.
Even effects of chemical exchange
on EPR spectra, which are treated only
barely or not at all in EPR textbooks,
are explained clearly. The more
demanding topic of spectra of systems
with more than one unpaired electron
requires more complicated mathematics
than the preceding chapters. Those
readers who dare to delve into this
treatment are rewarded by an explanation of all the basic concepts that are
needed for the analytical computation
of energy levels and transition dipole
moments. The final chapter on
approaches using perturbation theory
again involves an increase in mathemat-
ical complexity and requires a fairly
solid background in quantum mechanics. A reference to a suitable textbook
such as Levine+s Quantum Chemistry
would have been appropriate to make
this chapter more accessible to nonphysicists.
The short overview of advanced
techniques in the Appendix is unconvincing, as it does not explain the
potential of these techniques and does
not provide a very useful selection of,
and comment on, literature in this field.
Likewise, the very short treatment of
nitroxide spin labels in the chapter on
kinetic effects lacks a good list of
references, in particular to the series of
very informative books edited by Berliner and co-authors. Finally, an overview of programs for simulating EPR
spectra would have been useful, as many
readers will use the knowledge gained
from this book as a basis for working
with such programs.
Despite these slight shortcomings,
the selection of topics is well balanced.
A student who reads through this book
will acquire a solid repertoire of methods for interpreting even complicated
EPR spectra. The clear and basic first
chapters, and the fact that the complexity only increases gradually after that,
means that large parts of the book are
accessible to students with only a basic
mathematical and physical background.
For experienced researchers the book is
well suited as a dictionary of spectrum
analysis, as most types of problems are
illustrated by worked examples that
could easily be adapted to a new problem at hand. These examples can be
easily found through the book+s brief
but complete index. Although this book
may not be sufficiently comprehensive
to serve as the sole basis for a lecture
course on EPR spectroscopy, many of
the clear and simple figures are well
suited for illustrating lectures.
There are not many books that I
could recommend with such a good
conscience as this one. Personally, I
now regard it as an essential item on
my bookshelf.
Gunnar Jeschke
Lehrstuhl f+r Physikalische Chemie
Universit/t Konstanz (Germany)
DOI: 10.1002/anie.200785554
6 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2913
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