Table Of ContentMOLECULES IN PHYSICS, CHEMISTRY, AND BIOLOGY
TOPICS IN
MOLECULAR ORGANIZATION AND ENGINEERING
Honorary Chief Editor:
W. N. LIPSCOMB (Harvard, U.S.A.)
Executive Editor:
Jean MARUANI (Paris, France)
Editorial Board:
Henri AT LAN (Jerusalem, Israel) Alexandre LAFORGUE (Reims, France)
Sir Derek BAR TON (Texas, U.S.A.) J-M. LEHN (Strasbourg, France)
Christiane BONNELLE (Paris, France) P-O. LODWIN (Uppsala, Sweden)
Paul CAR 0 (Meudon, France) Patrick MacLEOD (Massy, France)
Stefan CHRISTOV (Sofia, Bulgaria) H. M. McCONNELL (Stanford, U.S.A.)
I. G. CSIZMADIA (Toronto, Canada) C. A. McDOWELL (Vancouver, Canada)
P-G. DE GENNES (Paris, France) Roy McWEENY (pisa, Italy)
J-E. DUBOIS (Paris, France) Ilya PRIGOGINE (Brussels, Belgium)
Manfred EIGEN (Gottingen, Germany) Paul RIGNY (Saclay, France)
Kenishi FUKUI (Kyoto, Japan) Ernest SCHOFFENIELS (Liege, Belgium)
Gerhard HERZBERG (Ottawa, Canada) R. G. WO OLLEY (Nottingham, U.K.)
Molecules in Physics,
Chemistry, and
Biology
Volume 3
Electronic Structure and Chemical Reactivity
Edited by
JEAN MARUANI
Centre de Mecanique Ondulatoire Appliquee,
Laboratoire de Chimie Physique,
CNRS and University of Paris, France.
Kluwer Academic Publishers
Dordrecht / Boston / London
Library of Congress Cataloging in Publication Data
Molecules in physics, chemsitry, and biology.
(Topics in molecular organization and engineering)
Includes bibliographies and indexes.
Contents: v. 1. General introduction to molecular
sciences -- -- v. 3. Electronic structure and
chemical reactivity.
1. Molecules. I. Maruani, Jean, 1937-
II. Series.
QC173.M645 1988 539' .6 88-6811
lSBN-13: 978-94-010-7783-5 e-lSBN-13: 978-94-009-2853-4
DOl: 10.1007/ 978-94-009-2853-4
Published by Kluwer Academic Publishers,
P.O. Box 17, 3300 AA Dordrecht, The Netherlands.
Sold and Distributed in the U.S.A. and Canada
by Kluwer Academic Publishers,
101 Philip Drive, Norwell, MA 02061, U.S.A.
In all other countries, sold and distributed
by Kluwer Academic Publishers Group,
P.O. Box 322, 3300 AH Dordrecht, The Netherlands.
All Rights Reserved
© 1989 by Kluwer Academic Publishers, Dordrecht, The Netherlands.
Softcover reprint of the hardcover 1s t edition 1989
No part of the material protected by this copyright notice
may be reproduced or utilized in any form or by any means,
electronic or mechanical including photocopying, recording or by
any information storage and retrieval system, without written
permission from the copyright owner
Table of Contents
Introduction to the Series / W. N. Lipscomb ix
Preface to Molecules in Physics, Chemistry, and Biology / Jean Maruani xiii
Preface to Volume 3 / Roy McWeeny xix
DENSITY FUNCTIONS AND ELECTRONIC STRUCTURE
The Molecule as a Many-Electron System: Electron Densities and Molecular
Properties / R. McWeeny 3
1. Introduction 3
2. Electron Density Functions 4
3. Electronic Properties - Response 8
4. Static Response to Uniform Fields 13
5 . Spin-Dependent Properties 18
6. Dynamic Response and Related Properties 22
7. Conclusion 28
References 29
Analysis of the Electronic Density as a Support of the Concepts of
Empirical Structural Chemistry / J. M. Garcia de la Vega, R. Lopez, J. R.
Alvarez Collado, J. Fernandez Rico, and J.I. Fernandez Alonso 31
1. Introduction 31
2. Partitioning of the Electronic Density 32
3. Results and Discussion 37
4. Atoms and Functional Groups 41
Acknowledgements 47
References 47
Molecules as Ensembles of Modified Atoms / Z. B. Maksic 49
1. Introduction 49
2. Modified Atoms in Molecules 51
3. Conclusion 69
Acknowledgements 69
References 69
The Physical Basis of the Lewis Electron Pair Model / R. F. W. Bader 73
I. The Challenge and Lewis Model 73
vi T ABLE OF CONTENTS
II. Properties of Density and Density Difference Functions 74
IIT. The Localization of Electrons 75
IV. The Laplacian of the Charge Density as a Basis for the Lewis
Model 80
V. Summary and Conclusions 90
Dedication 91
References 91
The Chemical Bond and Model Exchange-Correlation Potentials / R.
Gaspar and A Nagy 93
1. Introduction 93
2. The Hohenburg-Kohn Theorem and the Kohn-Sham Method 95
3. The Kinetic Energy Functional 97
4. The Exchange-Correlation Functional 98
5. Application to Chemical Systems 106
6. Problems and Prospects 107
References 108
Study of Chemical Bonding in Molecules: The Interest of Polarised
Neutron Diffraction / B. Gillon and J. Schweizer 111
1. Introduction 111
2. Polarised Neutron Diffraction 112
3. 3d Transition Metal Complexes 119
4. Organic Free Radicals 132
5. Conclusion 144
References 146
A Valence Concept for Molecular Structure and Reactions /Karl Jug 149
1. Historical Survey 149
2. Valence Index 150
3. Normal Valence versus Sub-and Hypervalence 159
4. Subvalence 161
5. Hypervalence 163
6. Geometry Changes 167
Acknowledgements 169
References 169
STRUCTURE AND REACTIVITY OF ORGANIC COMPOUNDS
On the Role of the Orbital Interaction Concept in the Interpretation of
Organic Free Radical Structures and Reactivities / Andrea Bottoni, Jacques
Fossey, and Daniel Lefort 173
1. Introduction 173
2. Theoretical Aspects 174
TABLE OF CONTENTS vii
3. Interpretation of Free-Radical Reactivities 185
4. A Quantitative PMO Analysis 196
5. Conclusion 214
References 215
Theoretical Studies on the Reactions of Free Radicals / J. J. Dannenberg 221
1. Introduction 221
2. Thermolysis of Azoalkanes 221
3. Bimolecular Radical Combinations 225
4. Disproportionations 228
5. Conclusion 230
References 231
Thermochemistry and Kinetics of Ionic and Radical Reactions in the Gas
Phase / G. Leroy, D. Peeters, M. Sana, and C. Wilante 233
1. Introduction 233
2. The Concept of Stabilization Energy 233
3. Thermochemistry and Kinetics of Elementary Processes 238
4. Rate Constant Calculations in Transition State Theory 252
5. Conclusions 255
Acknowledgement 256
References 256
Hydrocarbon Radical Cations in Condensed Phases / A. Lund, M.
Lindgren, S. Lunell, and J. Maruani 259
1. Introduction 259
2. Generation and Stabilization of Radical Cations 260
3. Experimental Results 264
4. Theoretical Calculations 284
Acknowledgements 296
References 296
Recent Developments in Calixarenes and their Properties / D. Gamet, M.
Bourakhouadar, Meublat, F. Leveiller, V. Bohmer, D. Jacquemain, J.
Vincens, and R. Perrin 301
1. Introduction 301
2. Synthesis of Calixarenes 303
3. Chemical Transformations of Calixarenes 311
4. Conformational Properties 318
5. Inclusion Complexes 323
6. Other Types of Calixarenes and Parent Molecules 331
7. Miscellaneous 334
8. Conclusion 334
References 334
viii TABLE OF CONTENTS
THEORETICAL APPROACHES TO CHEMICAL REACTIONS
The Reaction-Rate Approach in Physics, Chemistry, and Biology / S. G.
Christov 339
1. Introduction 339
2. General Theory 339
3. Applications to Gas-Phase Reactions 345
4. Applications to Dense-Phase Reactions 348
References 354
A Theoretical Study of the Unimolecular Dissociation of Diborane / John
F. Stanton, Rodney J. Bartlett, and William N. Lipscomb 357
1. Introduction 357
2. Methods 358
3. Calculations 359
4. Summary of Results 359
Acknowledgements 361
References 362
Mode Selective Biomolecular Reactions / J. Manz 365
1. Introduction: Why Mode Selective Chemical Reactions? 365
2. Hydrogen Atom plus Diatomic Molecule Reactions 367
3. Elementary Hydrogen Transfer Reactions 381
4. Conclusions 396
Acknowledgements 398
References 398
An Overview of the Theory of Chemical Reactions and Reactivity in
Enzymes and Solutions / O. Tapia 405
1. Introduction 405
2. Theory 406
3. Molecular Dynamics and Statistics of Reacting Systems 415
4. Conclusions and Perspectives 419
References 420
Index 423
Introduction to the Series
The Series 'Topics in Molecular Organization and Engineering' was initiated by
the Symposium 'Molecules in Physics, Chemistry, and Biology', which was held in
Paris in 1986. Appropriately dedicated to Professor Raymond Daudel, the
symposium was both broad in its scope and penetrating in its detail. The sections
of the symposium were: 1. The Concept of a Molecule; 2. Statics and Dynamics of
Isolated Molecules; 3. Molecular Interactions, Aggregates and Materials; 4.
Molecules in the Biological Sciences, and 5. Molecules in Neurobiology and
Sociobiology. There were invited lectures, poster sessions and, at the end, a
wide-ranging general discussion, appropriate to Professor Daudel's long and
distinguished career in science and his interests in philosophy and the arts.
These proceedings have been arranged into eighteen chapters which make up
the first four volumes of this series: Volume I, 'General Introduction to Molecular
Sciences'; Volume II, 'Physical Aspects of Molecular Systems'; Volume ill,
'Electronic Structure and Chemical Reactivity'; and Volume IV, 'Molecular
Phenomena in Biological Sciences'. The molecular concept includes the logical
basis for geometrical and electronic structures, thermodynamic and kinetic
properties, states of aggregation, physical and chemical transformations, specificity
of biologically important interactions, and experimental and theoretical methods
for studies of these properties. The scientific subjects range therefore through the
fundamentals of physics, solid-state properties, all branches of chemistry, bio
chemistry, and molecular biology. In some of the essays, the authors consider
relationships to more philosophic or artistic matters.
In Science, every concept, question, conclusion, experimental result, method,
theory or relationship is always open to reexamination. Molecules do exist!
Nevertheless, there are serious questions about precise definition. Some of these
questions lie at the foundations of modem physics, and some involve states of
aggregation or extreme conditions such as intense radiation fields or the region of
the continuum. There are some molecular properties that are definable only within
limits, for example, the geometrical structure of non-rigid molecules, properties
consistent with the uncertainty principle, or those limited by the neglect of
quantum-field, relativistic or other effects. And there are properties which depend
specifically on a state of aggregation, such as superconductivity, ferroelectric (and
anti), ferromagnetic (and anti), superfluidity, excitons, polarons, etc. Thus, any
molecular definition may need to be extended in a more complex situation.
Chemistry, more than any other science, creates most of its new materials. At
least so far, synthesis of new molecules is not represented in this series, although
the principles of chemical reactivity and the statistical mechanical aspects are
Jean Maruani (ed.), Molecules in Physics, Chemistry, and Biology, Vol. III, ix-x.
© 1989 by Kluwer Academic Publishers.
x INTRODUCTION TO THE SERIES
included. Similarly, it is the more physico-chemical aspects of biochemistry,
molecular biology and biology itself that are addressed by the examination of
questions related to molecular recognition, immunological specificity, molecular
pathology, photochemical effects, and molecular communication within the living
organism.
Many of these questions, and others, are to be considered in the Series 'Topics
in Molecular Organization and Engineering'. In the first four volumes a central
core is presented, partly with some emphasis on Theoretical and Physical
Chemistry. In later volumes, sets of related papers as well as single monographs
are to be expected; these may arise from proceedings of symposia, invitations for
papers on specific topics, initiatives from authors, or translations. Given the very
rapid development of the scope of molecular sciences, both within disciplines and
across disciplinary lines, it will be interesting to see how the topics of later volumes
of this series expand our knowledge and ideas.
WILLIAM N. LIPSCOMB
