Table Of ContentHORIZONS OF QUANTUM CHEMISTRY
ACADEMIE INTERNATIONALE
DES SCIENCES MOLECULAIRES QUANTIQUES
INTERNATIONAL ACADEMY
OF QUANTUM MOLECULAR SCIENCE
HORIZONS OF
QUANTUM CHEMISTRY
PROCEEDINGS OF THE THIRD INTERNATIONAL CONGRESS
OF QUANTUM CHEMISTRY HELD AT KYOTO, JAPAN,
OCTOBER 29 - NOVEMBER 3, 1979
Edited by
KENICHI FUKUI
Kyoto University, Dept. of Hydrocarbon Chemistry, Faculty of Engineering,
Kyoto, Japan
and
BERNARD PULLMAN
Institut de Biologie Physico-Chimique, Paris, France
D. REIDEL PUBLISHING COMPANY
DORDRECHT : HOLLAND / BOSTON: U.S.A.
LONDON: ENGLAND
Library of Congress Cataloging in Publication Data
International Congress of Quantum Chemistry, 3rd, Kyoto,
1979.
Horizons of Quantum Chemistry.
At head of title: International Academy of Quantum
Molecular Science.
Includes index.
1. Quantum chemistry-Congresses. I. Fukui,
Kenichi, 1918- II. Pullman, Bernard, 1919-
III. International Academy of Quantum Molecular Science.
IV. Title.
QD462.AI157 1979 541.2'8 80-12124
ISBN-13: 978-94-009-9029-6 e-ISBN-13:978-94-009-9027-2
DOl: 10.1007/978-94-009-9027-2
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TABLE OF CONTENTS
OPENING AND WELCOME ADDRESSES
K. Fukui vii
K. Husimi xi
Y. Yukawa xiii
P.-O. L6wdin xv
SYMPOSIUM I. NEW APPROACHES IN QUANTUM CHEMICAL
METHODOLOGY
Chairman: M. Kotani
M. Kotani
INTRODUCTION TO SYMPOSIUM I 3
R. G. Parr
DENSITY FUNCTIONAL THEORY OF ATOMS AND MOLECULES 5
O. Goscinski
SOME RECENT ADVANCES IN THE USE OF PROPAGATOR METHODS IN QUANTUM
CHEMISTRY. FROM AMO TO AGP 17
F. A. Matsen and C. J. Nelin
THE UNITARY GROUP FOffi1ULATION OF THE MANY-ELECTRON PROBLEM 37
SYI1POSIUM II. BOND FORMATION AND BREAKING
Chairman: M. Simonetta
til. Simonetta
BOND FO~1ATION AND BREAKING: THE HEART OF CHEMISTRY 51
R. F. W. Bader
QUANTUM TOPOLOGY 57
R. E. Wyatt
QUANTUM MECHANICAL STUDY OF CHEMICAL REACTION DYNAMICS 63
SYf-1POSIUM III. MOLECULAR INTERACTIONS
Chairman: J. Koutecky
J. Koutecky
INTRODUCTORY REMARKS TO SYMPOSIUM III: MOLECULAR INTERACTIONS 89
vi TABLE OF CONTENTS
R. K. Sparks, C. C. Hayden, K. Shobatake, D. M. Neumark,
and Y. T. Lee
MOLECULAR BEAM STUDIES OF REACTION DYNAHICS OF F + H2, D2 91
R. A. Marcus
INTRAMOLECULAR DYNAMICS: REGULAR AND STOCHASTIC VIBRATIONAL
STATES OF MOLECULES 107
D. P. Craig
INTERACTIONS BETWEEN CHIRAL MOLECULES: DISCRIMINATING INTERACTIONS 123
SYMPOSIUM IV. NEW FIELDS OF MOLECULAR SPECTROSCOPY
Chairman: J. A. Pople
J. A. Pople
NEW FIELDS IN MOLECULAR SPECTROSCOPY 147
T. Oka
MOLECULAR SPECTROSCOPY USING INFRARED LASERS:
A STUDY OF RADIATIVE AND COLLISIONAL PROCESSES 151
P. W. Atkins
MOLECULES AS SOURCES 169
SYMPOSIUM V. LARGE MOLECULES OF BIOLOGICAL IMPORTANCE
Chairman: R-O. L6wdin
F.-O. L6wdin
THE SIZE-CONSISTENCY PROBLEM FOR LARGE MOLECULES 193
A. Veillard, A. Dedieu and M.-M. Rohmer
THEORETICAL STUDIES OF THE STRUCTURE OF HEME MODELS 197
M. V. Basilevsky, G. N. Gerasimov, S. I. Petrochenko,
V. A. Tikhomirov
CALCULATIONS ON THE MECHANISM OF ION POLYMERIZATION IN CRYSTALS 227
K. Ohno
AB-INITIO COMPUTATIONS OF METAL-PORPHINE COMPLEXES 245
E. Clementi
THEORETICAL AND COMPUTATIONAL CHEMISTRY OF COMPLEX SYSTEMS 267
INDEX OF NA!1ES 281
INDEX OF SUBJECTS 289
OPENING ADDRESS
Kenichi Fukui
Kyoto University, Kyoto, Japan
Ladies and Gentlemen,
It was six years ago, in July, 1973, on the occasion of the First
International Congress of Quantum Chemistry in Menton that Professor
Daudel, then president of the International Academy of Quantum
Molecular Science, proposed having our 1979 meeting in Japan. When we
considered that proposal, we could not help feeling some hesitation,
because Japan is located in the so-called "far east", that is, far
from Europe and America where many scientists in our field live, so
that even on the basis of geography alone, it seemed that Japan was
not a suitable place for an international congress of this sort.
Nothing, therefore, gives me more pleasure than that various
adverse conditions have been overcome and we have here now so many
participants from abroad in addition to a great many Japanese
participants. Such a large number of quantum chemists and scientists
in related fields assembled in one place to exchange ideas about
recent topics! As it was with our previous two congresses, this is
a wonderful event in the development of quantum chemistry. To the
participants who energized this congress and put soul into it, I wish
in the first place to express my heartfelt gratitude. We are heavily
indebted to Professor Pullman and Professor Parr for this: they rendered
their good services for the convenience of participants from Europe and
America, as well as to Professor Daudel who prepared posters
distributed to institutions around the world to inform them of the
Kyoto Congress. I should also like to express appreciation to the
International Academy of Quantum Molecular Science, under whose
auspices this congress is held.
A distinguishing feature of this congress is its co-sponsorship
by the Science Council of Japan and the Chemical Society of Japan.
The former is an official organization of the Japanese Government, and
the latter is one of the largest scientific societies in Japan. This
sponsorship elevated the Congress and brought privileges and advantages
to its organizing.
vii
K. Fukui and B. Pullman (eds.), Horizons of Quantum Chemistry, vii - x.
Copyright © 1980 by D. Reidel Publishing Company.
viii OPENING ADDRESS
During the Congress, each morning is allotted to one symposium,
in which three or four invited lectures are scheduled. The proportion
of these invited lectures to the total contributed papers is large
compared to the usual case in international meetings. The chairmen
and the 17 lecturers accepting the requests of the Academy and the
organizers assisted in increasing the significance of the Congress.
In financial support to this congress, we received contributions
from a number of economic institutions, companies, and foundations.
Without this generous help, the Congress would not have been possible.
It was also fortunate that most of the symposium chairmen and invited
lecturers were able to obtain support from their own sources. And
Professor Lowdin kindly offered to publish contributed papers in the
International Journal of Quantum Chemistry as Proceedings of the
Congress. For all of these favours I am grateful beyond expressing.
The members of the Organizing Committee and the Sub-committees,
the Funds Committee, and the Finance Committee spent much time
organizing this congress, and we are indebted to the administration
bureaus of both the Science Council of Japan and the Chemical Society
of Japan for their hard work, as well as that of the Kyoto International
Conference Hall. Deep appreciation is due to all of these people.
I myself am firmly confident of the significance of this
international meeting, supported as it is by the good will and exertion
of so many people. But whether it is truly significant or not depends
also on what is contained in the meetings and what arises from them.
For the cooperation of all participants through their presentations and
discussion, and for the efforts of session chairpersons, I should like
to express thanks in advance.
Quantum chemistry has kept pace with the development of the
chemical sciences and now serves as a foundation in every area. This
is a logical consequence, and means that chemistry is developing as it
should. So an important question is: What position does quantum
chemistry actually hold now? We can, happily, make the following
statement: --- now, the chemist's dream of being able to calculate the
structure and property of a given compound or the velocity of a given
reaction with only paper and pencil is slowly but surely approaching
realization. In fact, the pertinent question now is, to what extent
will chemistry, which so far has been a science of a strongly empirical
nature, attain a nonempirical character? Simultaneously, it is now
time to ask, to what degree will the nonempirical character of quantum
chemistry be utilized for the purpose of advancing empirical chemistry?
In these ways quantum chemistry will function both theoretically
and methodologically. The remarkable recent progress of quantum
chemistry is of course mainly due to methodological advancement, but it
is also a result of improvements in physical measurement techniques and
in high-speed computers. We are so encouraged by these circumstances
as to unhesitatingly introduce quantum-chemical ways of thinking into
OPENING ADDRESS ix
every field of science which relates to chemical phenomena. The
propriety of such an idea will be obvious if you think, for instance,
what a great influence Professor Mulliken's concept of charge-transfer
has exerted on various fields of pure and applied science. Thus new
quantum-chemical concepts will accordingly be required to interpret
future discoveries. Conversely, it is even expected that new quantum
chemical ideas will lead to new discoveries. To be ready for this
event, our strenuous effo~t~are required. It will be helpful to
establish quantum-chemicaf~concepts as having distinct theoretical
bases, and efforts in this direction should soon be fruitful.
It may even happen that an idea born as a result of such efforts,
although it may be considered trifling by quantum chemists, will
entirely change the historical flow of chemistry. What is more, such
events will frequently occur from now on. Many jewels lie underground
to be discovered by our efforts. If young quantum chemists with big
dreams continue their research rigorously with confidence, outstanding
results will surely be obtained. And so at this tune I would like to
pass on my own dream, which I myself will never realize hereafter, to
the young participants in this congress.
Some of the most important future aspects of chemistry will
necessarily proceed in a nonempirical direction. The role of quantum
chemistry in such development will of course become more and more
important. I hope and expect that this congress will significantly
contribute to the development of chemistry in this direction.
At the same time, we must attend to unexplored branches of
chemistry, peripheral areas in particular. These can not be treated
by analogy from experience and they are far beyond nonempirical
rationalization. As a practical example, modern chemistry is faced
with the great task of treating various problems of earth and mankind.
In this connection, quantum chemical theories will produce new
principles concerning the conversion of materials and energies. It is
hoped that quantum chemists, not limited to this example, will become
carefully but boldly concerned with the multifarious problems in the
frontier fields. Quantum chemistry is expected to further strengthen
the connection between various fields of science other than chemistry,
thus deepening its interdisciplinary colour. Activity which is not
confined to the frame of chemistry would be desirable. In this sense
we expect the scope of discussions at this congress as well as the
meaning of "quantum chemistry" used here will never be understood only
in a limited or narrow sense.
On the basis of this idea, the prospects of quantum chemistry seem
to be bright and broad, heading toward a vast expanse like an ocean of
youthful energy. I believe not a few people agree with me that such
a view is not too optimistic.
To all participants, particularly those from abroad, I wish to
express a hearty welcome. We feel it our duty to exert ourselves during
x OPENING ADDRESS
this congress to demonstrate to you the significance of your attendance,
in return for your generous cooperation. May we all have a good and
frui t ful time.
Thank you for your attention!
WELCOME ADDRESS
K. Husimi, President of
Science Council of Japan
Mr. Chairman, Ladies and Gentlemen,
On the occasion of opening the Third International Congress of
Quantum Chemistry I am honored with the chance of saying a few words
on behalf of the sponsors.
First of all, I would like to extend my hearty welcome not only
to Prof. Lowdin, President of the International Academy of Quantum
Molecular Science and executive members of the Academy but also to all
the participating scientists in this Congress who have come over to
Japan from every continent. At the same time I cannot forget to express
my heartfelt thanks to all the people concerned for their cooperation
in arranging the Congress.
Chemistry is by nature an extensive discipline built up solely by
a series of accumulated results from experimental laboratory work on
chemical reaction. It belonged to a section of science characterized
as most empirical and, nevertheless, gave birth to the modern atomic
theory. When quantum mechanics appeared and developed to some extent,
the foundation was firmly laid on which the nature of interactions and
bindings of atoms and molecules could be accounted for solely on the
theoretical considerations. The significance of quantum mechanics to
chemistry is now accepted universally and provides a widely applicable
methodology for attacking the problems of chemical phenomena.
Chemistry and physics which had originally been brought up
differently from each other have become unified into the single
discipline of molecular science. In the center of this science is
placed quantum chemistry, which has more and more frequently has been
applied to wider range of problems including those encountered in
biology, pharmacy, medicine and engineering. Its development is really
remarkable.
This Congress will deal with such themes as recently developed
methods of quantum chemistry; newly cultivated sections of molecular
fusion, fission and reciprocal action; remarkably expanded area of
xi
K. Fukui and B. Pulli1Uln (eds.), Horizons of Quantum Chemistry, xi - xii.
Copyright © 1980 by D. Reidel Publishing Company.
