Electron Spin Resonance PDF
Preview Electron Spin Resonance
Electron 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 ~ 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
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