Table Of ContentContributors
Sten Andersson T. J. McLarnan
Werner H. Baur Murli H. Manghnani
I. D. Brown L. C. Ming
D. de Fontaine P. B. Moore
L. W. Finger Alexandra Navrotsky
R. M. Hazen E. Parthé
F. Hulliger J. M. Sanchez
John C. Jamieson R. D. Shannon
Friedrich Liebau James B. Thompson, Jr.
Structure
and Bonding
in Crystals
Volume II
Edited by
Michael O'Keeffe
Alexandra Navrotsky
Department of Chemistry
Arizona State University
Tempe, Arizona
1981
ACADEMIC PRESS
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COPYRIGHT © 1981, BY ACADEMIC PRESS, INC.
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United Kingdom Edition published by
ACADEMIC PRESS, INC. (LONDON) LTD.
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Library of Congress Cataloging in Publication Data
Main entry under title:
Structure and bonding in crystals.
Includes bibliographies and index.
1. Solid state chemistry. 2. Crystallography.
3. Chemical bonds. I. O'Keeffe, Michael.
II. Navrotsky, Alexandra.
QD478.S77 541'.0421 81-7924
ISBN 0-12-525102-5 (v. 2) AACR2
PRINTED IN THE UNITED STATES OF AMERICA
81 82 83 84 9 8 7 6 5 4 3 2 1
List of Contributors
Numbers in parentheses indicate the pages on which the authors' contributions begin.
S ten Andersson (233), Inorganic Chemistry 2, Chemical Center, University of
Lund, S-220 07 Lund 7, Sweden
Werner H. Baur (31), Department of Geological Sciences, University of Illinois,
Chicago, Illinois 60680
/. D. Brown (1), Institute for Materials Research, McMaster University, Hamilton,
Ontario L8S 4M1, Canada
D. de Fontaine (117), Department of Materials Science and Mineral Engineering,
University of California, Berkeley, Berkeley, California 94720
L. W. Finger (109), Geophysical Laboratory, Carnegie Institution of Washington,
Washington, D. C. 20008
R. M. Hazen (109), Geophysical Laboratory, Carnegie Institution of Washington,
Washington, D. C. 20008
F. Hulliger (297), Laboratorium fur Festkôrperphysik, ΕΤΗ, CH-8093 Zurich,
Switzerland
John C. J amie son (95), Department of Geophysical Sciences, University of
Chicago, Chicago, Illinois 60637
Friedrich Liebau (197), Mineralogisches Institut der Christian-Albrechts-
Universitàt, 2300 Kiel, Federal Republic of Germany
T. J. McLarnan (133), Department of Chemistry, University of Chicago, Chicago,
Illinois 60637
Murli H. Manghnani (95), Hawaii Institute of Geophysics, University of Hawaii,
Honolulu, Hawaii 96822
L. C. Ming (95), Hawaii Institute of Geophysics, University of Hawaii, Honolulu,
Hawaii 96822
xi
xii List of Contributors
P. B. Moore (133), Department of Geophysical Sciences, University of Chicago,
Chicago, Illinois 60637
Alexandra Navrotsky (71), Department of Chemistry, Arizona State University,
Tempe, Arizona 85281
E. Parthé (259), Laboratoire de Cristallographie aux Rayons X, Université de
Genève, CH-1211 Geneva 4, Switzerland
J. M. Sanchez (117), Department of Materials Science and Minerai Engineering,
University of California, Berkeley, Berkeley, California, 94720
R. D. Shannon (53), Central Research and Development Department, Ε. I. du Pont
de Nemours & Co. Experimental Station, Wilmington, Delaware 19898
James B. Thompson, Jr. (167), Department of Geological Sciences, Harvard Uni
versity, Cambridge, Massachusetts 02138
Preface
The last few years have witnessed a remarkable convergence of interest
in the structure and bonding in crystals with complex structures. Physi
cists have developed methods of dealing with the electronic and other
properties of the increasingly complex solids that have been found to have
unusual properties and that are being used in device technology. Solid
state chemists have shown a renewed interest in synthesis — sparked, in
part, by the development of new techniques for structure investigation.
Geoscientists at the same time have found that the new insights into
structure and bonding in silicates are tremendously useful to mineralogy
and earth physics.
Before this renaissance, virtually the only guide to the factors determin
ing crystal structure was the principles set out in the early days of solid
state chemistry and put in definitive form in the chemists "bible"—
Pauling's "Nature of the Chemical Bond." Indeed in dealing with com
plex silicates, it is little exaggeration to state that there had been little
progress (until recently) since the formulation of the celebrated "Pauling's
Rules" 50 years ago.
In January 1980, we took the opportunity of this golden anniversary to
convene a diverse group of scientists with a common interest in principles
of structure and bonding in complex solids, to discuss and assess recent
development. The meeting (generously supported by the Solid State
Chemistry program of the National Science Foundation [grant DMR-
xiii
xiv Preface
7827019] and by the Center for Solid State Science at Arizona State Uni
versity) brought together solid state physicists and chemists, metallur
gists, ceramists, and geologists, who found that not only did they have
common interests, but often spoke similar languages.
These volumes are a direct outgrowth of that meeting; virtually all the
contributors were participants, although the books are by no means "con
ference proceedings." In the light of their experience at the meeting, the
contributors were encouraged to present an overview of their fields of
research and its bearing on related fields.
We benefited greatly from the presence of Linus Pauling—he was al
ways ready with penetrating questions and comments. In addition, he pre
sented a delightful ad lib account of the early days of crystal chemistry,
particularly at Pasadena, and this is recorded, essentially verbatim, here.
Chemists have long had the intuition that atoms retain, in some sense,
their own special identity in compounds. To the solid state chemist at
least, one of the more interesting advances in solid state physics has been
the development of atomic pseudopotentials and the discovery that they
could be applied directly to atoms in crystals. The first few chapters (1-7)
reflect this approach in which the electronic properties of the isolated
atoms are used to make useful and often rather exact calculations and
predictions of the structure, stability, and properties of solids of many
different types.
A related and parallel development has been the discovery that the
methods of the "molecular" chemists (MO theory, etc.) lend themselves
rather readily and revealingly to the discussion of solids; a related group
of chapters (8-12) discusses recent developments in these fields.
There is new understanding too of the older topics such as bond length,
bond strength, ionic radii, etc., and some of these developments are de
scribed in chapters 13-19. These concepts have been used by geochemists
and geophysicists to systematize and predict phase transitions at high
pressure, as the last three papers in this section discuss.
A final group of chapters (19-26) deals with the problems of classifying
complex solids and with systematic descriptions of the relationships be
tween their structures. This is a particularly important problem when
structures and sometimes stoichiometries are at first sight apparently very
complex, but when "correctly" described are much easier to appreciate
and understand.
We are indebted to our colleagues both for making very helpful sug
gestions and for graciously accepting editorial input to their contributions.
Preface xv
Pamela O'Keeffe and a number of A.S.U. students and research asso
ciates helped enormously in transporting the meeting participants from
Phoenix to the desert oasis of Castle Hot Springs, and in many other
ways.
Michael O'Keeffe
Alexandra Navrotsky
Contents of Volume I
1 Historical Perspective
LINUS PAULING
2 Quantum Theory and Crystal Chemistry
J. C. PHILLIPS
3 Pseudopotentials and Crystal Structure
MARVIN L. COHEN
4 Quantum-Defect Orbital Radii and the Structural
Chemistry of Simple Solids
AARON N. BLOCH AND GINA C. SCHATTEMAN
5 A Pseudopotential Viewpoint of the Electronic and
Structural Properties of Crystals
ALEX ZUNGER
6 Elementary Quantitative Theory of Chemical
Bonding
WALTER A. HARRISON
Contents of Volume I
7 The Role and Significance of Empirical and
Semiempirical Correlations
LEO BREWER
8 Theoretical Probes of Bonding in the Disiloxy
Group
MARSHALL D. NEWTON
9 A Comparison of Experimental and Theoretical
Bond Length and Angle Variations for Minerals,
Inorganic Solids, and~Molecules
G. V. GIBBS, E. P. MEAGHER, M. D. NEWTON, AND
D. K. SWANSON
10 The Role of Nonbonded Forces in Crystals
M. O'KEEFFE AND B. G. HYDE
11 Molecules within Infinite Solids
JEREMY K. BURDETT
12 Charge Density Distributions
ROBERT F. STEWART AND MARK A. SPACKMAN
13 Some Aspects of the Ionic Model of Crystals
M. O'KEEFFE
