Computational Methods for Large Molecules and Localized States in Solids: Proceedings of a Symposium, Held May 15–17, 1972, at the IBM Research Laboratory, San Jose, California

386 Pages·1973·4.12 MB·English

by  A. H. Eschenfelder (auth.), Frank Herman, A. D. McLean, R. K. Nesbet (eds.)

COMPUTATIONAL METHODS FOR
LARGE MOLECULES AND
LOCALIZED STATES IN SOLIDS
THE IBM RESEARCH SYMPOSIA SERIES
1971: Computational Methods in Band Theory
Editors: P.M. Marcus, J. F. Janak, and A.R. Williams
1972: Computational Solid State Physics
Editors: F. Herman, N. W. Dalton, and T. R. Koehler
1972: Sparse Matrices and Their Applications
Editors: D. J. Rose and R. A. Willoughby
1972: Complexity of Computer Computations
Editors: R. E. Miller and J. W. Thatcher
Associate Editor: J. D. Bohlinger
1973: Computational Methods for Large Molecules
and Localized States in Solids
Editors: F. Herman, A. D. McLean, and R. K. Nesbet
COMPUTATIONAL METHODS FOR
LARGE MOLECULES AND
LOCALIZED STATES IN SOLIDS
Proceedings of a Symposium, Held May 15-17,1972,
at the IBM Research Laboratory, San Jose, California
Edited by
F. Herman, A. D. McLean, and R. K. Nesbet
Large-Scale Scientific Computations Department
IBM Research Laboratory, San Jose, California
~ PLENUM PRESS • NEW YORK-LONDON • 1973
Library of Congress Catalog Card Number 72-93442
ISBN-13: 978-1-4684-2015-9 e-ISBN-13: 978-1-4684-2013-5
DOl: 10.1007/978-1-4684-2013-5
© 1973 Plenum Press, New York
Softcover reprint of the hardcover 1s t edition 1973
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N.Y. 10011
United Kingdom edition published by Plenum Press, London
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All rights reserved
No part of this publication may be reproduced in any form without
written permission from the publisher
PREFACE
During the past few years, there has been dramatic progress in
theoretical and computational studies of large molecules and local-
ized states in solids. Various semi-empirical and first-principles
methods well known in quantum chemistry have been applied with
considerable success to ever larger and more complex molecules,
including some of biological importance, as well as to selected
solid state problems involving localized electronic states. In-
creasingly, solid state physicists are adopting a molecular point
of view in attempting to understand the nature of electronic states
associated with (a) isolated structural and chemical defects in
solids; (b) surfaces and interfaces; and (c) bulk disordered solids,
most notably amorphous semiconductors.
Moreover, many concepts and methods already widely used in
solid state physics are being adapted to molecular problems. These
adaptations include pseudopotentials, statistical exchange approxi-
mations, muffin-tin model potentials, and multiple scattering and
cellular methods. In addition, many new approaches are being de-
vised to deal with progressively more complex molecular and local-
ized electronic state problems.
In view of these developments, IBM San Jose Research Laboratory,
in conjunction with IBM World Trade Corporation, organized a re-
search symposium on the application of the computational methods of
quantum chemistry and solid state physics to the study of electronic
properties of complex molecules, localized imperfections in solids,
and disordered condensed systems. Dr. Frank Herman served as
Symposium Chairman. The present volume consists of papers pre-
sented at this symposium, which was held on May 15 to 17, 1972 at
the IBM San Jose Research Laboratory.
An important purpose of this symposium was to bring together
active workers in theoretical chemistry and solid state theory for
an exchange of ideas and methodology across the communication
barrier that has traditionally separated these two disciplines.
In both of these fields theoretical and computational methods have
v
vi PREFACE
reached a high level of sophistication, and most theoreticians, for
natural reasons, normally work within the framework of only one of
these disciplines.
The organizers of this symposium believe that such meetings
are essential for minimizing provincialism, for making people
aware of techniques used in one area which may be ready for ex-
ploitation in another, and for exploring in depth the regions that
overlap. The subject of provincialism in science is considered
further in the Banquet Speech by Professor George S. Hammond. One
of the highlights of the symposium was a panel discussion at which
representatives of many different schools of thought presented
their views and compared notes. This panel discussion is reproduced
in the present volume.
The papers included here address the following topics:
(a) scientific goals and challenges for computational studies of
complex molecules and localized states in solids;
(b) effectiveness of different approaches to these goals;
(c) discussion of relative accuracy and practicality of traditional
methods of quantum chemistry;
(d) potential applications of new computational methods directed
specifically to complex molecules and localized states in solids;
(e) discussion of areas of research requiring a synthesis of
molecular and solid state concepts, for example, exciton states in
molecular crystals, biological macromolecules, polymers, molecules
in crystalline environments, localized defects in crystals, surface
states, and localized states in disordered solids.
The organizers of this symposium are indebted to many persons
who have contributed to its success. We are particularly grateful
to Dr. Andrew H. Eschenfelder, IBM San Jose Research Laboratory and
Mr. G~ry S. Kozak, IBM World Trade Headquarters, New York for their
encouragement and financial support; and Mr. Warren C. Edwards,
IBM San Jose Research Laboratory, for his expert handling of the
local arrangements.
We are also grateful to many of our colleagues within the IBM
World Trade Corporation for their cooperation in bringing selected
speakers and participants to the symposium. We are particularly
grateful to the following: Mr. P. de Blanpre, IBM France; Mr. L. O.
Bunk a , IBM Canada; Mr. O. Cilius-Nielsen, IBM Denmark; Mr. F. G.
Insinger and Mr. J. A. van der Pool, IBM Netherlands; Mr. R. Jacqmin,
IBM Belgium; Mr. J. S. Nist, IBM Mexico; Mr. J. J. Peppercorn. ~r.
PREFACE
S. Quigley, and Mr. C. Squire, IBM United Kingdom; Dr. P. Schweitzer,
IBM Germany; Mr. A. Serrano, IBM Spain; Dr. J. Vogel, IBM Switzer-
land; and Mr. G. Wethal, IBM Norway. We are also indebted to Drs.
William J. Turner and Bernard J. van der Hoeven, IBM Research, York-
town Heights for administrative support; and Mr. Robert N. Ubell,
President, Plenum Publishing Corporation, for his cooperation.
Finally, we are indebted to many of our colleagues at IBM San
Jose Research Laboratory for their important contributions. In
particular, thanks are due to Miss Colleen de Long, Mrs. Linda
Lopez, Mrs. Jacqueline Mendenhall, and Mrs. Patricia B. Rodgers for
extensive typing and editorial assistance; Mrs. Rodgers again for
transcribing the tape recordings of the symposium; Mr. Jack De Lany,
Mr. Brad Hall, and Mrs. Lorraine Riddle for artistic and graphics
support; and Mr. Rick W. Kipp, Mr. Rudy M. Martinez and Mr. Donald
E. Schreiber for help with the visual aids.
This effort can be considered a success if the symposium and
the present volume help to open up channels of communication between
quantum chemists and theoretical solid state physicists.
Frank Herman, A. D. McLean, and R. K. Nesbet
Symposium Proceedings Coeditors
CONTENTS
WELCOMING REMARKS 1
A. H. Eschenfelder
1. Scientific Challenges I
INTRODUCTORY REMARKS 5
R. S. Mulliken
QUANTUM CHEMISTRY. THEORY OF GEOMETRIES AND . . . . . . 11
ENERGIES OF SMALL MOLECULES
J. A. Pople
ORGANIC TRANSITION STATES 23
L. Salem
SOLID STATE CONCEPTS IN RADIATION CHEMISTRY 29
AND BIOLOGY
G. W. Robinson
MOLECULAR MODELING BY COMPUTER . . . . . . . . . . . . . 49
W. A. Little
2. Scientific Challenges II
INTRODUCTORY REMARKS 57
J. A. Barker
STRUCTURAL CHARACTERISTICS AND ELECTRONIC STATES . . . • 59
OF HEMOGLOBIN
M. Weissbluth
MOLECULAR THEORY OF NUCLEATION . . . 67
J. W. Corbett, H. L. Frisch, D. Peak
and M. St. Peters
ix
x CONTENTS
3. Computational Methods I
APPROXIMATIONS FOR LARGE-MOLECULE CALCULATIONS 81
F. E. Harris
AB INITIO COMPUTATION OF MOLECULAR STRUCTURES 87
THROUGH CONFIGURATION INTERACTION
P. S. Bagus, B. Liu, A. D. McLean and
M. Yoshimine
APPROXIMATE METHODS IN QUANTUM CHEMISTRY 117
M. C. Zerner
LCAO-MO CLUSTER MODEL FOR LOCALIZED STATES 133
IN COVALENT SOLIDS
G. D. Watkins and R. P. Messmer
DESCRIPTION OF MOLECULES IN TERMS OF 149
LOCALIZED ORBITALS
K. Ruedenberg
4. Computational Methods II
INTRODUCTORY REMARKS 159
P. S. Bagus
THE SCF-Xa SCATTERED-WAVE METHOD .. . . . 161
K. H. Johnson, J. G. Norman, Jr., and
J.W.D. Connolly
THE ORBITAL CORRECTION METHOD 203
W. A. Harrison
PANEL DISCUSSION ON COMPUTATIONAL METHODS . . • • . • 209
Panel Members: P. S. Bagus, F. E. Harris, W. A.
Harrison, K. H. Johnson, A. D. McLean, U. T.
Mueller-Westerhoff, K. Ruedenberg, G. A. Segal,
H. S. Taylor, G. D. Watkins, and M. C. Zerner
Discussion from Floor: T. L. Gilbert, R. K.
Nesbet, J. A. Pople, and L. Salem
AB INITIO SCF CALCULATIONS OF THE CARBAZOLE AND 229
2,4,7-TRINITRO-9-FLUORENONE (TNF) MOLECULES
I. P. Batra and H. Seki
CONTENTS xi
5. Localized States
and Disordered Solids I
SURFACE STATES AND LEED . . 235
P. M. Marcus and D. W. Jepsen
WANNIER FUNCTIONS 245
W. Kohn
DEVELOPMENTS IN LOCALIZED PSEUDOPOTENTIAL METHODS 251
P. W. Anderson and J. D. Weeks
LOCALIZED DEFECTS IN SEMICONDUCTORS 261
F. L. Vook and K. L. Brower
TRANSMISSION OF ELECTRONS THROUGH A DISORDERED 275
ARRAY OF POTENTIALS
P. Erd8s and R. C. Herndon
6. Localized States
and Disordered Solids II
INTRODUCTORY REMARKS 293
D. Henderson
ELECTRONIC STRUCTURE OF AMORPHOUS SEMICONDUCTORS 295
D. Weaire and M. F. Thorpe
SOME POLYTYPES OF GERMANIUM AND A TIGHT BINDING . . . . 317
MODEL FOR THE ELECTRONIC STRUCTURE OF AMORPHOUS SOLIDS
D. Henderson and I. B. Ortenburger
COEXISTENCE OF LOCALIZED AND EXTENDED STATES? 327
S. Kirkpatrick and T. P. Eggarter
CLUSTER SCATTERING IN AMORPHOUS SEMICONDUCTORS 341
AND LIQUID METALS
J. Keller
PROPERTIES OF LOCALIZED STATES IN . . . . . . . . . . • 357
DISORDERED MATERIALS
K. F. Freed
7. Banquet Speech
ARE THERE CULTS OF THEORETICIANS? . . 375
G. S. Hammond