Essays in Structural Chemistry

501 Pages·1995·14.28 MB·English

by  J. W. Linnett (auth.), A. J. Downs, D. A. Long, L. A. K. Staveley (eds.)

ESSAYS IN STRUCTURAL CHEMISTRY
DR L. A. WOODWARD
Essays in
Structural Chemistry
Edited by
A. J. DOWNs-Inorganic Chemistry Laboratory, University of Oxford
D. A. LONG-SchoolofChemistry, University of Bradford
L. A. K. STAVELEY-Inorganic Chemistry Laboratory, University of Oxford
PLENUM PRESS
NEW YORK
© A.J. Downs, D. A. Long, L. A. K. Staveley, 1971
First published 1971
Softcover reprint of the hardcover I st edition 1971
All rights reserved. No part of this publication may be
reproduced or transmitted, in anyform or by any means,
without permission.
u.s. edition published by Plenum Press, a
division of Plenum Publishing Corporation,
227 West 17th Street, New York, N.Y. 10011.
ISBN-13: 978-1-4684-1904-7 e-ISBN-13: 978-1-4684-1902-3
001: 10.1007/978-1-4684-1902-3
Library of Congress Catalog Card Number 76-144136
These essays are presented to
L. A. WOODWARD
on the occasion of his retirement
by some of his colleagues and former students
Contents
EDITORIAL FOREWORD '(iii
PREFACE xv
CHAPTER 1 Molecular Coree fields and valency 1
J. W. LINNETI', Department of Physical Chemistry,
University of Cambridge
A. Introduction
B. Determination of force constants
C. The valence force field
D. Examples of the use of force constants
CHAPTER 2 The hyper RaJnan e&"ect 18
D. A. LONG, School of Chemistry, University of Bradford
A. Introduction
B. The origin of the hyper Raman effect
C. Classical treatment
D. Density matrix treatment
E. Selection rules, symmetry and activity
F. Experimental
Appendix
CHAPTER 3 Vibrational assigmnents in smalllDolecules 56
W. H. FLETCHER, Department of Chemistry, University of
Tennessee
A. Introduction
B. General principles
C. Linear molecules
vii
Vlll CONTENTS
D. Prolate symmetric tops
E. Oblate symmetric tops
F. Spherical tops
G. Asymmetric tops
H. Force fields and vibrational assignments
I. Conclusions
CHAPTER 4 Interferometry: Experimental techniques and
appllcations to inorganic structures 91
G. W. CHANTRY, National Physical Laboratory,
Teddington
A. Introduction
B. Interferometric methods in the far-infrared region
C. Some practical examples
CHAPTER 5 Single-crystal and high-temperature gas-phase
Raman spectroscopy III
I. R. BEATTIE, Department of Chemistry, University of
Southampton
A. Introduction
B. High-temperature gas-phase Raman spectroscopy
C. Single-crystal Raman spectroscopy
CHAPTER 6 High-resolution Raman spectroscopy of gases 135
H. G. M. EDWARDS, School of Chemistry, University of
Bradford
A. Introduction
B. Historical development
C. Experimental arrangement and advent of laser sources
D. The determination of structural parameters
E. Theory and examples of rotational Raman spectra
F. Future perspectives
CHAPTER 7 Intermolecu1ar force effects in the Raman
spectra of gases 163
C. G. GRAY, Department of Physics, University of Guelph,
Ontario, AND H. L. WELSH, McLennan Physical
Laboratories, University of Toronto
A. Introduction
B. The effect of pressure on line and band shapes
C. Frequency shifts due to isotropic intermolecular forces
CONTENTS IX
CHAPTER 8 Raman spectra of alkali halides 189
R. S. KRIsHNAN, Department of Physics, Indian Institute
ofS cience, Bangalore
A. Introduction
B. Historical background
C. Experimental technique
D. Theoretical considerations
E. Raman spectra-Theoretical considerations
F. Experimental results
G. Mixed crystals and crystals doped with impurities or
defects
H. Future trends
CHAPTER 9 Atomic interactions in molecular, covalent,
ionic and metallic crystals 227
SAN-ICIDRO MIZUSHIMA AND lSAO ICHISHIMA, Tokyo
Research Institute, Yawata Iron and Steel Co., Kawasaki-City
A. Introduction
B. Molecular crystals
-C. Covalent and ionic crystals
D. Types of atomic aggregate and the Periodic Table
E. Basic nature of metallic crystals
F. Atomic aggregates with closed d-shells
G. Crystal structure and cohesive energy oft ransition metals
H. Contribution of d-electrons to the atomic aggregation of
transition elements
I. Crystal structure and cohesive energy of lanthanides
J. The nature of 3d- electrons and the transformation of Fe
K. Conclusion
CHAPTER 10 Structural aspects of the Mossbauer eft'ect 244
J. F. DUNCAN, Chemistry Department, Victoria University
of Wellington
A. Introduction
B. Method
C. Applications in chemistry
D. Conclusions
CHAPTER 11 Non-stoichiometry in 8uorite structures 264
L. E. J. ROBERTS, Atomic Energy Research Establishment,
Harwell
A. Introduction
B. Anion-excess phases
C. Anion deficient phases
x CONTENTS
CHAPTER 12 Some aspects of solvation 296
H. J. V. TYRRELL, Department of Chemistry, Chelsea
College ofS cience and Technology
A. Introduction
B. Thermodynamic aspects of solvation
C. Transport coefficients and solvation
D. Nuclear magnetic resonance spectroscopy and solvation
E. Conclusions
CHAPTER 13 Vibrational spectroscopic studies of complexes
in SOIUtiOD 327
D. N. WATERS, Department ofC hemistry, Brunei University
A. Introduction
B. Quantitative equilibrium studies
C. Structural aspects; solvent effects and solution inter-
actions
D. Structural aspects; individual complexes
CHAPTER 14 Vibrational studies of the Jahn-Teller effect 355
J. A. CREIGHTON, University Chemical Laboratory,
University of Kent, Canterbury
A. Introduction
B. Vibrational properties of electronically degenerate
molecules
C. Experimental results: strong Jahn-Teller effects
D. Experimental results: weakJahn-Teller effects
E. Conclusion
CHAPTER 15 Spectroscopic properties of the diatomic oDeles
of the transition elements 383
R. F. BARROW, Physical Chemistry Laboratory, University
ofOiford
A. Introduction
B. Methods of study
C. Properties of the ground states
D. Electronic transitions
E. Hyperfine structure
F. Conclusions
CONTENTS D
CHAPTER 16 Vibrational studies or metal-metal bondiag 404
M. J. WARE, Department of Chemistry, University of
Manchester
A. Introduction
B. Characteristics of metal-metal vibrations
c. Interpreted spectra
D. Force constants and other bond parameters
CHAPTER 17 Infrared and Raman spectra or organometallic
and related compounds 433
J. R. HALL, Department of Chemistry, University of
Queensland
A. Introduction
B. Linear dimethylmetal compounds
C. Methyl-platinum(IV) compounds
D. Trisilyl compounds of Group V elements
E. Trigermyl compounds of Group V elements
CHAPTER 18 Structural aspects or sulphur-fluorine
chemistry 457
H. L. ROBERTS, Mond Division, Imperial Chemical
Industries, Runcom
A. Introduction
B. Hexavalent sulphur fluorides
C. Tetravalent sulphur fluorides
D. Divalent sulphur fluorides