Applied Quantum Chemistry: Proceedings of the Nobel Laureate Symposium on Applied Quantum Chemistry in Honor of G. Herzberg, R. S. Mulliken, K. Fukui, W. Lipscomb, and R. Hoffman, Honolulu, HI, 16–21 December 1984

439 Pages·1986·26.355 MB·English

by  Kenichi Fukui (auth.), Vedene H. Smith Jr., Henry F. Schaefer III, Keiji Morokuma (eds.)

Applied Quantum Chemistry
Applied
Quantum Chemistry
Proceedings of the Nobel Laureate Symposium
on Applied Quantum Chemistry
in Honor of G. Herzberg, R. S. Mulliken, K. Fukui,
W. Lipscomb, and R. Hoffman,
Honolulu, HL 16-21 December 1984
Edited by
Vedene H. Smith, Jr.
Department oj Chemistry,
Queen's University, Kingston, Ontario, Canada
Henry F. Schaefer III
Department oj Chemistry,
University oj California, Berkeley, California, U. S.A.
and
Keiji Morokuma
Institute jor Molecular Science,
Myodaiji, Okawki, Japan
D. REIDEL PUBLISHING COMPANY
A MEMBER OF THE KLUWER ACADEMIC PUBLISHERS GROUP
DORDRECHT/BOSTON/LANCASTER/TOKYO
library of Congress Cataloging in Publication Data
Nobel Laureate Symposium on Applied Quantum Chemistry
(1984 : Honolulu, Hawaii)
Applied quantum chemistry.
Includes index.
I. Quantum chemistry-Congresses. J. Herzberg, Gerhard,
1904- . II. Smith, Vedene H. III. Schaefer, Henry F.
IV. Morokuma, K. (Keiji), 1934- . V. Title.
QD462.AIN57 1984 541.2'8 86-17868
ISBN-13: 978-94-01()'8609-7 e-ISBN-13: 978-94-D09-4746-7
001: IO.lOO7I978-94-D09-4746-7
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TABLE OF CONTENTS
Preface
Reminiscences - My Forty Years' Study of Chemical Reactions
K. Fukui
Intuition and Quantum Chemistry
S.R. Ovshinsky 27
Potential Energy Surfaces and the Rates of the Reaction
OH + OH --+ H20 + 0
T. Fueno 33
An Aspect of Electron Delocalization in Chemical Reactions
Hiroshi Fujimoto 43
Reaction Topology
Paul G. Mezey 53
Molecular Conformations and Potential Energy Surface
Topology
I.G. Csizmadia and J.G. Angyan 75
Quantum Chemical Studies on Reaction Mechanism
and Reaction Path
R.Z. Liu 85
Multi-Reference Cluster Expansion Theory and an Interaction
of Hydrogen Molecule with Palladium
H. Nakatsuji and M. Hada 93
Very Accurate Coupled Cluster Calculations for Diatomic
Systems with Numerical Orbitals
L. Adamowicz and R.J. Bartlett III
Well-Tempered Gaussian Basis Sets in SCF and MC SCF
Calculations on N2 and P2
M. Klobukowski and S. Huzinaga 135
Ab-Initio Molecular Orbital Studies of Structure and
Reactivity of Transition Metal-OXO Compounds
K. Yamaguchi, Y. Takahara and T. Fueno 155
vi TABLE OF CONTENTS
Applications of the LCGTO Local Spin Density Method
D.R. Salahub 185
The Structural Rule of Mo-Fe-S Cluster Compounds
Au-chin Tang, Qian-shu Li and Chia-chung Sun 213
The Protonic Counterpart of Electronegativity and Its
Relationship to Electronic and Protonic Hardness
Lawrence L. Lohr 223
Bonding and Reactivity of Tungstenacyclobutadiene
Complexes
Jerome K. Silvestre and Thomas A. Albright 231
The Reaction Path of HNO(lA,,) Formation from H and NO
O. Nomura, S. Ikuta and A. 19awa 243
Structures, Stability, and Reactivity of Doubly Bonded
Compounds Containing Silicon or Germanium
S. Nagase, T. Kudo and K. Ito 249
Binary SN Ring Systems and Related Heterocyclothiazenes
W.G. Laidlaw and M. Trsic 269
On the Uranium-to-Carbon Bonds in CP3UL Complexes
K. Tatsumi and A. Nakamura 299
Proton Affinity of Germane (GeH4): The Chemical Bond of
its Protonated Species (GeH5+)
S. Ikuta, S.K. Sudoh, S. Katagiri and O. Nomura 313
Chemical Bonding and the Nature of Glass Structure
J. Bicerano and S.R. Ovshinsky 325
Theoretical Study of the Conformational Properties and
Torsional Potential Functions of Polyalkylmethacrylate
Polymers
B.C. Laskowski, R.L. Jaffe and A. Komornicki 347
A Theoretical Study of Short S ... O "Non-Bonded" Interactions
P. Becker, C. Cohen-Addad, B. Delley, F.L. Hirshfeld
and M.S. Lehmann 361
Quantum Chemical Interpretation of Oxidation Number with
Ab Initio Molecular Orbital Wavefunctions
K. Takano, H. Hosoya and S. Iwata 375
Charge Distributions and Chemical Effects. XLI. Alkane
Atomic Charges in Energy Calculations
S. Fliszar, J.-M. Leclercq, C. Mijoule and S. Odiot 395
TABLE OF CONTENTS vii
Theoretical Investigations of the Ammonium Radicals NH4,
ND4 and NT4: Ground State Stability and Rydberg Transitions
J. Kaspar, V.H. Smith, Jr. and B.N. McMaster 403
An Ab Initio Calculation of Vibrational States of the
H30+ Ion
N. Shida, K. Tanaka and K. Ohno 421
Vibrational Frequencies of Small Metal Clusters. The
Beryllium Tetramer
R. Murphy and H.F. Schaefer III 431
Index 439
PREFACE
This volume constitutes the proceedings of the Nobel Laureate
Symposium on Applied Quantum Chemistry held during the International
Chemical Congress of Pacific Basin Societies, 16-21 December 1984, in
Honolulu, Hawaii. The Symposium was held in honour of the five Nobel
Laureates who have contributed so extensively to the development of
Applied Quantum Chemistry. K. Fukui, G. Herzberg, R. Hoffmann,
W.N. Lipscomb and R.S. Mulliken. Professors Fukui, Hoffmann and
Lipscomb attended and presented plenary lectures to the Symposium.
Their lectures and the other invited papers and invited poster
presentations brought into focus the current state of Applied Quantum
Chemistry and showed the importance of the interaction between quantum
theory and experiment.
We are indebted to the Subdivision of Theoretical Chemistry and
the Division of Physical Chemistry of the American Chemical Society,
the Division of Physical Chemistry of the Chemical Institute of Canada,
Energy Conversion Devices, Inc., the IBM Corporation, and the Congress
for their financial support which helped to make the Symposium
possible.
We would like to thank Dr. Philip Payne for making some of the
local arrangements, and Mrs. Betty McIntosh for her assistance in
arranging the Symposium and in the preparation of these proceedings
for publication.
Vedene H. Smith, Jr. Henry F. Schaefer III Keiji Morokuma
REMINISCENCES
--- MY FORTY YEARS' STUDY OF CHEMICAL REACTIONS
Renichi Fukui*
Kyoto Institute of Technology
Matsugasaki-Hashigamicho, Sakyo-ku
Kyoto 606, Japan
ABSTRACT A scientific biography of K. Fukui as one of
the inquirers into the "chemical reaction" is presented in
the form of a narrative story. The emphasis is placed on
the circumstances of developments and applications of the
frontier orbital concept and the intrinsic reaction
coordinate approach.
INTRODUCTION
Good Morning, Ladies and Gentlemen.
I feel greatly privileged to talk at this symposium.
To do so is also a great pleasure, of course, and my
pleasure would be much greater, if I were here still as an
active researcher. Actually, I retired from Kyoto
University in April, 1982 due to the age-limit regulation,
and am now an administrator at a national university in
Kyoto. Such an age-limit system is very common in national
universities in Japan, and is uniformly applied to everyone
without exception. My present job is really pleasant and
enjoyable, but you can easily imagine that this new job is
not convenient for research. I have no laboratory, no
staff, no more young students working with me, and have very
little time to spend for research. I cannot see my
scientific journals without going to my former Department
which is a few kilometers away from my present office. So,
it is difficult for me to keep pace with you all in reading
new scientific papers, and in commenting or discussing new
topics. That is the reason why this morning I am talking
essentially about past things, and I hope you will forgive
my intention in doing so.
*
Also belongs to : Institute for Fundamental Chemistry,
15 Morimoto-cho, Shimogamo, Sakyo-ku, Kyoto 606, Japan
I
V. H. Smith. Jr. et al. (eds.). Applied Quantum Chemistry. /-25.
© /986 by D. Reidel Publishing Company.
2 K. FUKUI
EXPERIMENTAL STUDIES, 1940-45
My research life started with experimental studies in
1940 when I was a third year student at Kyoto University.
The subject of my studies was the reaction of paraffin
hydrocarbons with antimony pentachloride. A paraffin
molecule having tertiary carbon atoms reacted with SbCIS to
form an orange-red precipitate, which after awhile converted
itself to tarry matter after vigorous evolution of HCI gas,
and if ethyl ether was added to that, it turned into a
beautiful deep blue solution. On the other hand such a
distinctive color reaction was not seen in paraffins with no
tertiary carbon atoms, and the former behavior was
attributed to the initial formation of a carbonium ion. The
remarkable difference in reactivity between a tertiary
carbon and a secondary or primary carbon atom attracted my
deep interest. Incidentally, such reactivity problems of
paraffin hydrocarbons were treated theoretically more than
twenty years later by myself with my colleagues.
I
I
I I
C C
It SbClS I
- --C-C-H ---c-i:fi
I I
C C
I I
I I
I ct: tertiary c~rbon atom
My second experimental work on hydrocarbon chemistry
was the isomerization of n-butene to isobutene, which was
carried out in 1942-1943. I learned that the migration of
methyl group was facilitated by the electron deficiency in
the double bond caused by the action of heterogeneous acidic
catalysts. This study went well and brought me a prize in
1944 when I was 25 years old.
i i
H H
3 3
HC=CH-CH3 I H2C=C-CH3
H4P207
Again incidentally, this problem appeared before my eyes
later as an example of the reaction generally called "[1,2]
sigmatropic shift" in the terminology of the Woodward
Hoffmann rule [1].
a two-electron cycle
REMINISCENCES - MY FORTY YEARS' STUDY OF CHEMICAL REACTIONS
BIRTH OF THE FRONTIER ORBITAL CONCEPT
The fact that I had been studying hydrocarbon chemistry
as my specialty had a close connection with the birth of my
frontier orbital concept. The reason was that the then
prevailing "electronic theory" was not a suitable means for
explaining the reactivity of hydrocarbons where the electric
charge distribution in the molecule is almost uniformly
zero. Such a situation drew my· attention particularly to
aromatic hydrocarbons in which an interesting "orientation"
problem had already been well known in organic chemistry.
I calculated simply the Huckel molecular orbital,
coefficients of the highest occupied molecular orbital (MOl
of several aromatic hydrocarbons. The figures represented
well the reactive positions in electrophilic aromatic
substitutions. This particular orbital was named as the
"frontier orbital". This paper appeared in the Journal of
Chemical Physics in 1952 [2], the same year Prof. Mulliken's
important paper on the theory of charge-transfer
complexation appeared in the Journal of American Chemical
Society [3]. This Mulliken paper was illuminating to me in
interpreting my result as an electron delocalization between
molecules [4].
Encouraged by this interesting result, an extension to
the nucleophilic reaction was attempted. In this case the
lowest unoccupied MO played the role of the frontier
orbital. In radical substitutions both of these orbitals
cooperated as the frontier orbitals [5]. A recently
calculated contour diagram of the highest occupied MO of
naphthalene is indicated in Figure 1.
Orientation in the
nitration of naphthalene.
Figure 1. The highest occupied MO of naphthalene.