Table Of ContentMethods in
Computational Chemistry
Volume 5
Atomic and
Molecular Properties
METHODS IN COMPUTATIONAL CHEMISTRY
Volume 1 Electron Correlation in Atomsand Molecules
Edited by Stephen Wilson
Volume 2 Relativistic Effects in Atoms and·Molecules
Edited by Stephen Wilson
Volume 3 Concurrent Computation in Chemical Calculations
Edited by Stephen Wilson
Volume 4 Molecular Vibrations
Edited by Stephen Wilson
Volume 5 Atomic and Molecular Properties
Edited by Stephen Wilson
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Methods
in
Computational Chemistry
Volume 5
Atomic and
Molecular Properties
Edited by
STEPHEN WRSON
Rutherford Appleton Labaratory
Oxfordshire, England
Springer Science+Business Media, LLC
Library of Congress Cataloging in Publication Data
(Revised for volume 5)
Methods in computational chemistry.
Computer disk (5\4 in.) in pocket of v. 2; requires IBM PC AT, 386. or compatible
machine; 640K RAM; MS-DOS; double-sided, high density (l.2M) disk drive; 8087
arithmetic processor.
lncludes bibliographies and indexes.
Contents: v. 1. Electron correlation in atoms and molecules-[etc.]-v. 4. Molecular
vibrations-v. 5. Atomic and molecular properties.
1. Chernistry-Data processing. I. Wilson, S. (Stephen). 1950-
QD39.3.E46M47 1987 542 87-7249
ISBN 978-1-4899-1641-9 ISBN 978-1-4899-1639-6 (eBook)
DOI 10.1007/978-1-4899-1639-6
©Springer Science+Business Media New York 1992
Originally published by Plenum Press, New York in 1992.
Softcoverreprint ofthe bardeover 1st edition 1992
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, rnicrofilrning,
recording, or otherwise, without written perrnission from the Publisher
Contributors
Karol Jankowski, Institute of Physics, Nicholas Copernicus University,
87-100 Torun, Poland
Ann-Marie Märtensson-Pendrill, Department of Physics, University of
Göteborg and Chalmers University of Technology, S-412 96 Göteborg,
Sweden
B. T. Pickup, Department of Chemistry, University of Sheffield, Sheffield
S3 7HF, England
Stephen Wilson, Rutherford Appleton Laboratory, Chilton, Oxfordshire,
OXll OQX, England
From the Preface to Volume 1
Today the digital computer is a major tool of research in chemistry and the
chemical sciences. However, although computers have been employed in
chemical research since their very inception, it is only in the past ten or
fifteen years that computational chemistry has emerged as a field of research
in its own right. The computer has become an increasingly valuable source
of chemical information, one that can complement and sometimes replace
more traditional laboratory experiments. The computational approach to
chemical problems can not only provide a route to information that is not
available from laboratory experiments but can also afford additional insight
into the problern being studied, and, as it is often more efficient than the
alternative, the computational approach can be justified in terms of
economics.
The applications of computers in chemistry are manifold. A broad over
view of both the methods of computational chemistry and their applications
in both the industrial research laboratory and the academic research environ
ment is given in my book Chemistry by Computer (Plenum Press, 1986).
Applications of the techniques of computational chemistry transcend the
traditional divisions of chemistry-physical, inorganic, and organic-and
include many neighboring areas in physics, biochemistry, and biology.
Numerous applications have been reported in fields as diverse as solid
state physics and pesticide research, catalysis and pharmaceuticals, nuclear
physics and forestry, interstellar chemistry and molecular biology, and sur
face physics and molecular electronics. The range of applications continues
to increase as research workers in chemistry and allied fields identify prob
lems to which the methods of computational chemistry can be applied.
The techniques employed by the computational ehernist depend on the
size of the system being investigated, the property or range of properties of
vii
viii From the Preface to Volume 1
interest, and the accuracy to which these properties must be measured. The
methods of computational chemistry range from quantum-mechanical stud
ies of the electronic structure of small molecules to the determination of bulk
properties by means of Monte Carlo or molecular dynamics simulations;
from the study ofprotein structures using the methods ofmolecular mechan
ics to the investigation of simple molecular collisions; from expert systems
for the design of synthetic routes in organic chemistry to the use of computer
graphics techniques to investigate interactions between biological molecules.
The computers employed in chemical calculations vary enormously,
from the small microcomputers used for data analysis to the large state-of
the-art machines that are frequently necessary for contemporary ab initio
calculations of molecular electronic structure. Increasingly, large mainframe
computers are departing from the traditional von Neumann architecture
with its emphasis on serial computation, and a similar change is already
underway in smaller machines. With the advent of vector processing and
parallel processing computers, the need to match an algorithm closely to the
target machine has been recognized. Whereas different implementations of
a given algorithm on traditional serial computers may Iead to programs that
differ in speed by a factor of about 2, factors of 20 were not uncommon
with the first vector processors, and larger factors can be expected in the
future.
With the increasing use of computational techniques in chemistry, there
is an obvious need to provide specialist reviews of methods and algorithms
so as to enable the effective exploitation of the computing power available.
This is the aim of the present series of volumes. Each volume will cover a
particular area of research in computational chemistry and will provide a
broad-ranging yet detailed analysis of contemporary theories, algorithms,
and computational techniques. The series will be of interest to those whose
research is concerned with the development of computational methods in
chemistry. More importantly, it will provide an up-to-date summary of com
putational techniques for the chemist, atomic and molecular physicist,
biochemist, and molecular biologist who wish to employ the methods to
further their research programs. The series will also provide the graduate
student with an easily accessible introduction to the field.
Preface
Atomic and molecular electronic structure calculations provide in the first
instance approximations to wave functions, electron densities, and total
energies. Experiments frequently explore the effect of some extemal pertur
bation, for example, an applied electric or magnetic field, on the particular
system being studied. The study of atomic and molecular properties, there
fore, provides an important bridge between theoretical and computational
investigations of the electronic structure of atoms and molecules and experi
mental Observations.
This volume is concemed with the theoretical determination of atomic
and molecular properties. Property calculations are often very computation
ally demanding, requiring a precision beyond that which may be acceptable
in electronic energy studies. These calculations may, for example, involve
the use of sophisticated approaches to the electron correlation problern as
weil as very extended and flexible basis sets. In the first chapter of the present
volume, Karol Jankowski provides a comprehensive review of the effects of
electron correlation on atomic properties. The calculation of P- and T
violating properties in atoms and molecules is discussed in the second chapter
by Ann-Marie Märtensson-Pendrill. In Chapter 3, Barry T. Pickup provides
a masterly description of not only the theory of molecular properties but
also the computation aspects of practical applications. Finally, in Chapter 4,
the Rayleigh-Schrödinger perturbation theory and many-body perturbation
theory of atomic and molecular properties are described by the editor.
It seems certain that the calculation of atomic and molecular properties
will assume increasing importance in the years ahead as the techniques of
computational quantum chemistry find an ever wider range of application.
Together, the four chapters in this volume provide a broad-ranging yet
thorough analysis of the most important aspects of contemporary research
ix
X Preface
into the theoretical and computational study of the properties of atoms and
molecules.
Stephen Wilson
Wood End
