Table Of ContentElectron Spin Resonance
Volume 106
A Specialist Periodical Report
Electron Spin Resonance
Volume IOB
A Review of Recent Literature to mid-1986
Senior Reporter
M. C. R. Symons, Department of Chemistry,
University of L eicester
Reporters
J. F. Gibson, Imperial College, London
G. R. Hanson, Monash University, Australia
C. P. Keijzers, University of Nijmegen, The Netherlands
R. P. Mason, National Institute of Environmental Health Sciences,
North Carolina, USA
C. Mottley, Luther College, Iowa, USA
J. R. Pilbrow, Monash University, Australia
A. Schweiger, ETH-Zentrum, Zurich, Switzerland
The Royal Society of Chemistry
Burlington House, London, W I V OBN
ISBN 0-85 186-85 1-7
ISSN 0305-9578
Copyright 0 1987
The Royal Society of Chemistry
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means graphic, electronic,
~
including photocopying, recording, taping or
information storage and retrieval systems without
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written permission from The Royal Society of Chemistry
Printed in Great Britain at the Alden Press, Oxford,
London and Northampton
Foreword
This is the Inorganic and Bio-inorganic half of Volume 10. Volume 10A was
concerned with organic and bio-organic e.s.r. spectroscopy and its major
'Contents' are listed herein for the benefit of those who have not seen this
Volume. In particular, I call attention to the Chapters on Spin-Labels and on
Free Radical Studies in Biology and Medicine whjch may well be of interest to
readers of the present Volume. Also, the review on Loop-gap Resonators is, of
course, particularly relevant.
A.
The only Chapter 'missing' is one on 'Theoretical Aspects' by Dr. Hudson
who was, unfortunately, unable to prepare it in time. This is now scheduled for
Volume 11A since theory is equally applicable for either volume.
As I mentioned in Volume 10A, there remains the question of viability of
these Volumes. Every effort is being made for rapid publication and to keep the
price reasonable. All we can hope for is that those who value this production
will do their best to ensure that their institutes and friends buy copies so
that we can continue with what I hope is a really valuable contribution to the
e.s.r. literature.
I am most grateful to all the authors for surmounting all sorts of problems
in order to get their contributions to me on time. It is so easy to agree to
writing a Review a year or so before it is due - one forgets the very
considerable task that this actually represents - so I am very appreciative of
the efforts made by my collaborators.
Martyn C. R. Symons
Cont ents
CHAFTER 1 Spin - Spin Interactions in Weakly Interacting Dimers
By C.P. Keijzers
1 Introduction 1
2
Spin-Hamiltonian
3 5
Isotropic Exchange
3.1 5
Spin-Hamiltonian
3.2 J 6
Analytical Expressions for
3.2.1 Localized Method 7
3.2.2 10
Molecular Orbital Method
3.2.3 11
The Above Approaches
3.3 Experimental Determinations of J 11
3.3.1 Merging Effect 12
3.3.2 Susceptibility with EPR 12
3.3.3 Singlet - Triplet Mixing 13
3.3.4 14
ENDOR
3.3.5 14
Undiluted Compounds with Small Exchange
3.3.6 Heteronuclear Dimers 15
3.3.7 Ferromagnetic Coupling 16
3.3.8 Cluster Systems 16
3.3.9 Paramagnetic Host Crystals 18
3.4 Calculation of J 18
4 20
The Zero Field Splitting Tensor
-
4.1 Analytical Expressions for us 21
4.1.1 The Dipole - Dipole Interaction 21
4.1.2 The Spin - Orbit Contribution 22
4.2 25
Experimental
28
5 Antisymmetric Exchange
-+
29
5.1 Analytical Expression of d
5.1.1 The Dipole - Dipole Interaction 29
5.1.2 The Spin - Orbit Contribution 29
5.2 32
Experimental
35
References
vii
... Contents
Vlll
CHAFTER 2 Transition-metal Ions
By J.F. Gibson
39
1 Introduction
2 40
General
42
Theory
45
Analysis of Spectra, Computing
Jahn - Teller Effects 47
49
Mixed Valence Complexes
51
Phase Transitions
54
Paramagnetic Ligands
Binuclear and Oligonuclear Complexes 55
3 s = 1/2 61
61
d1 Configuration
61
Tervalent Titanium, Zirconium and Hafnium
62
Quadrivalent Vanadium, Niobium and Tantalum
64
Quinquevalent Chromium and Molybdenum
66
Sexivalent Manganese, Technetium and Rhenium
66
d5 Configuration
66
Zerovalent Vanadium and Univalent Chromium
68
Bivalent Manganese, Tervalent Iron, Ruthenium and Osmium
69
Quinquevalent Platinum
d7 69
Configuration
69
Univalent Iron and Bivalent Cobalt
70
Tervalent Nickel, Palladium and Platinum
d9 72
Configuration
72
Bivalent Copper
75
Zerovalent Cobalt and Univalent Nickel
4 S = l 77
2
77
Configuration
77
Univalent Cobalt and Divalent Nickel
5 S = 3/2 77
d3 Configuration 77
77
Tervalent Chromium and Quadrivalent Rhenium
