THE NEW WORLD OF QUANTUM CHEMISTRY
ACADEMIE INTERNATIONALE
DES SCIENCES MOLECULAIRES QUANTIQUES
INTERNATIONAL ACADEMY
OF QUANTUM MOLECULAR SCIENCE
THE NEW WORLD OF
QUANTUM CHEMISTRY
PROCEEDINGS OF THE SECOND INTERNATIONAL CONGRESS
OF QUANTUM CHEMISTRY HELD AT NEW ORLEANS, U.S.A.,
APR ILl 9 _ 2 4, 1976
Edited by
BERNARD PULLMAN
lnstitut de Biologie Physico-Chimique, Fondation Edmond de Rothschild, Paris
and
ROBERT PARR
Chemistry Department, University of North Carolina, Chapel Hill, U.S.A.
D. REIDEL PUBLISHING COMPANY
DOll.DRECHT-HOLLAND / BOSTON-U.S.A.
Library of Congress Cataloging in Publication Data
International Congress of Quantum Chemistry, 2d, New
Orleans, 1976.
The new world of quantum chemistry.
At head of title: International Academy of Quantum
Molecular Science.
Includes bibliographies.
1. Quantum chemistry-Congresses. I. Pullman,
Bernard, 1919II. Parr, Robert G., 1921III. International Academy of Quantum Molecular Science.
IV. Title.
QD462.A1I57 1976
541'.28
76-43051
e-ISBN-13:978-94-010-1523-3
ISBN -13:978-94-010-1525-7
DOl: 10.1007/978-94-010-1523-3
Published by D. Reidel Publishing Company,
P.O. Box 17, Dordrecht, Holland
Sold and distributed in the U.S.A., Canada and Mexico
by D. Reidel Publishing Company, Inc.
Lincoln Building, 160 Old Derby Street, Hingham,
Mass. 02043, U.S.A.
All Rights Reserved
Copyright
© 1976 by D. Reidel Publishing Company, Dordrecht, Holland
Softcover reprint of the hardcover 1st edition 1976
No part of the material protected by this copyright notice may be reproduced or
including photocopying, recording or by any informational storage and
utilized in any form or by any means, electronic or mechanical
retrieval system, without written permission from the copyright owner
TABLE OF CONTENTS
Prof. B. Pullman
OPENING REMARKS
ACKNOWLEDGMENTS
VII
IX
SYMPOSIUM I - FOUNDATIONS OF QUANTUM CHEMISTRY
(Chairman: K. Ruedenberg)
R. McWeeny
PRESENT STATUS OF THE CORRELATION PROBLEM
R. Daudel
QUANTUM MECHANICAL FACETS OF CHEMICAL BONDS
Y. Ohm
PROPAGATOR THEORY OF ATOMIC AND MOLECULAR STRUCTURE
3
33
57
SYMPOSIUM II - MOLECULAR SCATTERING
(Chairman: J.O. Hirschfelder)
J.O. Hirschfelder
QUANTIZED VORTICES IN MOLECULAR SCATTERING
81
W.H. Miller
RECENT DEVELOPMENTS IN SEMICLASSICAL MECHANICS:
EIGENVALUES AND REACTION RATE CONSTANTS
87
R.D. Levine
ENERGY CONSUMPTION AND ENERGY DISPOSAL IN ELEMENTARY
CHEMICAL REACTIONS
103
SYMPOSIUM III - QUANTUM ORGANIC CHEMISTRY AND BEYOND
(Chairman: B. 'Pullman)
B. Pullman
INTRODUCTION
133
VI
TABLE OF CONTENTS
G.G. Hall
COMPUTATIONAL METHODS FOR LARGE MOLECULES
137
A. Pullman
THE SOLVENT EFFECT: RECENT DEVELOPMENTS
149
R.E. Christoffersen and R.P. Angeli
QUANTUM PHARMACOLOGY
189
SYMPOSIUM IV - POTENTIAL SURFACES, TRANSITION STATES,
AND INTERMEDIATES IN CHEMICAL AND PHOTOCHEMICAL PROCESSES
(Chairman: M. Karplus)
S.D. Peyerimhoff and R.J. Buenker
CALCULATION OF POTENTIAL SURFACES FOR GROUND AND EXCITED
STATES
213
Salem
TRANSITION STATES AND REACTION MECHANISMS IN ORGANIC
CHEMISTRY
241
1.
SYMPOSIUM V - SURFACE QUANTUM CHEMISTRY AND CATALYSIS
(Chairman: K. Fukui)
K. Fukui
INTRODUCTORY REMARKS ON THE QUANTUM THEORY OF CATALYSIS
AND RELATED SURFACE PHENOMENA
273
J. Koutecky
METHODS FOR SURFACE QUANTUM CHEMISTRY
279
J. R. Schrieffer
THE CHEMISORPTION BOND
305
K.H. Johnson
MOLECULAR CLUSTERS AND CATALYTIC ACTIVITY
317
OPENING REMARKS
Professor Bernard PULLMAN
President of the International Academy
of Quantum Molecular Science
Ladies and Gentlemen, my dear colleagues,
It is a 8reat honor and pleasure for me to inaugurate officiall~ the 2~ International Congress of Quantum Chemistry. Like
the 1 t one which was held 3 years ago in Menton, France, this
Congress is organized under the auspices of the International
Academy of Quantum Molecular Science. It translates into action
one of the major aims of the Academy which is to stimulate contacts, collaboration and friendship between quantum-molecular
scientists at the International level, whatever be their fields
of interest. At this particular period when the scientific exchanges become rather difficult, because of the strong increase
in the costs of transportation and an unfortunate concommitant
decrease in the funds available from public sources for scientific
research in general, this gathering of quantum molecular scientists of widely distributed interests seems an especially wellcome venture. The development of the applications of quantummechanical concepts, theories and methodologies to broader and
new fields of exploration is a continuous and striking phenomenon.
Considered originally as limited essentially to the field of chemistry, the quantum theories are now flowing freely through biology, pharmacology, solid state physics etc. From studies of molecules in free space they evoluate more and more towards the
study of molecules in their environments. The programm of the present meeting testifies to this extension and broadening. We do not
doubt that the encounters which will occur here, the exchanges of
ideas and informations will stimulate new developments and new
collaborations.
It is my pleasant duty to thank my colleagues of the Scientific Organizing Commitee of the Academy for their efforts and cpl-
VIII
OPENING REMARKS
laboration in the establishment of the scientific program. Our
next t.hanks are due to the Executive Commitee of the Congress and
in particular to its chairman, Prof. Robert Parr, for the extre·mely efficient action which they have conducted for the sake of
this organization and to the success of which many of us owe the
possibility of being here. I believe that it may be more judicious to reserve for the closing session of the Congress the expression of our appreciation to the Local Commitee and especially
to its chairman, Prof. Politzer, for what looks like a most entertaining and rich program of social and cultural events.
Because of the material difficulties that I mentioned earlier, we are less numerous here than we expected to be. Those of
us who are present feel therefore particularly priviledged. We
hope that this situation will have the possible advantage of enabling deeper discussions and closer associations. I wish you all
a profitable and pleasant stay.
Institut de Biologie Physico-Chimique
Laboratoire de Biochimie Theorique
associe au C.N.R.S.
13, rue P. et M. Curie - 75005 Paris -
ACKNOWLEDGMENTS
Generous grants in support of this Congress were received from
the National Science Foundation, the Petroleum Research Fund of the
American Chemical Society, and the Energy Research and Development
Administration.
The United States Air Force kindly arranged trans-
portation for two invited speakers from Europe, through its Window
on Science Program.
Thanks also are due to several of the invited
speakers for arranging their travel expenses from other sources,
and to the Hewlett-Packard Corporation for sponsoring our first
coffee break.
I thank my fellow Executive Committee members, Professors John
Pople, Klaus Ruedenberg and Peter Politzer, for much help in
preparation for the Congress.
Professor Politzer's contribution was
enormous, for making the wonderful local arrangements.
In this he
was assisted by Professors Basil Anex and Robert Flurry, to whom we
also are grateful.
The Congress Secretary, Mrs. Shirley Ritter, labored hard toward
the success of the Congress, for over a year.
A very special thanks
to her.
ROBERT G. PARR
Chairman of the Executive Committee
SYMPOSIUM I. FOUNDATIONS OF QUANTUM CHEMISTRY
Chairman
R. Ruedenberg
Department of Chemistry,
Iowa State University
Ames, Iowa, U.S.A.
PRESENT STATUS OF THE CORRELATION PROBLEM
R. McWeeny
Department of Chemistry, The Um versi ty ,
Sheffield, U.K.
1.
Introduction
Almost exactly 10 years ago, at the Slater Symposium on
Sanibel Island, I gave a review lecture [1] on "The Nature of
Electron Correlation in Molecules". Since that time the output of
papers and review articles on the so-called "correlation problem"
has continued undiminished, but new perspectives have emerged and
work in this area has, to some extent, been overshadowed by
advances in other fields. To quote from a recent review [2]
"Nowadays about 90\ of the quantum-mechanical calculations on
molecules are performed by the self-cons1stent-field (SCF) method,
using more or less extended sets of basis functions, without any
consideration of the possible effects of correlation". There are,
no doubt, two main reasons for this trend: (i) the ready availability of efficient SCF programmes, and (ii) the totally
unexpected success of the resultant Hartree-Fock (or near-HartreeFock) wave functions as a means of predicting molecular properties
at a quantitative level. Nevertheless, even if it might now be
considered a minority interest, important work on electron
correlation is in progress and until it has reached fruition,
probably within the next decade, "chemical accuracy" for systems
of moderate size w~ll not be achieved. It is therefore again
opportune to attempt a reappraisal and an exposition of current
trends.
2.
What is correlation?
Even the concept of electron correlation presents difficulties:
it may be approached in terms of the energy difference between an
independent-particle.l1lodel (in which, by definition, correlation
B. Pullman and R. Parr (eds.), The New World of Quantum Chemistry, 3-31.All Rights Reserved.
Copyright © 1976 by D. Reidel Publishing Company, Dordrecht-Holland.