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Book Review Cohesion A Scientific History of Intermolecular Forces. By John S. Rowlinson

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Books
Cohesion
A Scientific History of Intermolecular Forces. By
John S. Rowlinson.
Cambridge University Press,
Cambridge 2002.
333 pp., hardcover £ 65.00.—
ISBN 0-52181008-6
Why does matter stick together? Why
do gases condense to liquids, and liquids
freeze to solids? Rowlinson“s book
provides a detailed historical account
of how some of the leading scientists of
the past three centuries have tried to
answer these questions. The topic of
cohesion and the study of intermolecular forces have been important components of the chemical and physical
sciences for hundreds of years. Although
great progress has been made in the last
twenty years, our understanding of
“cohesion” is still far from being complete. Thus the definition of “intermolecular forces” in encyclopedias is fuzzy:
“Intermolecular forces are forces that
are exerted by molecules on each other
and that, in general, affect the macroscopic properties of the material of
which the molecules are a part. Such
forces may be either attractive or repulsive in nature.”
However, this book summarizes in a
magnificent way the intensive efforts
that have been made to understand the
phenomenon of cohesion. Reasonable
progress in our understanding had
already been made in earlier centuries,
but it is not always clear who was first
and to whom the credit belongs. In this
respect Rowlinson has made careful
3066
choices. Thus, for example, he points
out that some less famous scientists
came up with brilliant ideas. Or that
two scientists had a good idea at the
same time but did not know about each
other)s studies. He demonstrates nicely
that in the 18th and even in the 19th
century the flow of information or lack
of it was a serious problem and could
have decisive effects on scientific
careers.
The structure of this book is straightforward. It is organized into four broad
periods of advances in our understanding of intermolecular forces. The first
three are associated with scientific
giants such as Newton, Laplace, and
van der Waals. Their names provide the
titles of these chapters. Subchapters
describe fundamental work during particular time periods, by important scientists, or on special topics. The final
section deals with the 20th century and
gives an account of the successful use of
classical and quantum mechanics to
resolve most of the remaining problems.
In this respect it became important at
the end of the 1950s to develop a
theoretical model for the intermolecular
potential, to use in computer simulations of molecular systems. An assembly
of such molecules is “created” in the
computer memory, and the physical
state of the system is found either by
solving Newton)s equations of motion to
see how the system evolves with time, or
by using a weighted sampling method
(the MC method) that generates molecular configurations with the same frequency of occurrence as is found in such
a model fluid at equilibrium. Such
simulations were used to generate
pseudo-experimental values for macroscopic physical properties such as density, vapor pressure, energy, and heat
capacity for systems with an assumed
intermolecular potential. Hitherto the
testing of any theory of liquids or dense
gases had been a hazardous business
because of the uncertainty in our knowledge of the intermolecular potential.
Rowlinson emphasizes that despite our
still inadequate knowledge of the intermolecular potential these methods are
used to calculate the behavior of large
biomolecular systems and to solve other
complex problems. Axilrod and Teller,
who introduced a three-body potential,
found that the pair-wise additive
, 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
approach is inadequate and that manybody interactions have to be taken into
account. The development of further
intermolecular potentials is described in
detail. This part of the book emphasizes
the excitement of science, which is no
doubt due to the fact that the author
himself was deeply involved in this
business.
Rowlinson gives a nice account of
how, beside argon, water became the
most important molecule for simulation
studies. Water is unique in its importance and in its properties. No other
substance has been the subject of so
much study and speculation, nor been
harder to understand at the molecular
level. Recent progress by Saykally and
Leforestier on the experimental determination of a pair potential illustrates
the complexity of the problem: their
pair potential for heavy water, D2O, is
based on one originally derived from
quantum-mechanical calculations and
has no less than 72 parameters. Consequently, Rowlinson asks: “How far do
these beautiful spectroscopic studies
help us to understand the cohesion of
liquid water or of other liquids for which
it is possible to determine the multidimensional potential surfaces of the
dimer?” The success of work on the
water dimer raises hopes, but in 2003
there seems to be still some way to go.
The successful Car – Parrinello molecular dynamics simulations (CPMD),
along with path integral methods, may
be a great step forward, but unfortunately those methods are not discussed
in this book.
The book will be primarily of interest to physical chemists and chemical
physicists, as well as to historians of
science interested in the origins of our
modern understanding of cohesion. University libraries are strongly recommended to buy this beautiful book.
Ralf Ludwig
Fachbereich Chemie
Physikalische Chemie
Universitt Dortmund (Germany)
Angew. Chem. Int. Ed. 2003, 42, 3066 – 3067
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