Mössbauer Spectroscopy and Transition Metal Chemistry

292 Pages·1978·15.401 MB·English

by  Prof. Dr. Philipp Gütlich, Dr. rer. nat. Rainer Link, Prof. Dr. Alfred X. Trautwein (auth.)

Inorganic Chemistry Concepts
Volume 3
Editors
Margot Becke Christian K. J ~rgensen
Michael F. Lappert Stephen J. Lippard
John L. Margrave Kurt Niedenzu
Robert W. Parry Hideo Yamatera
Philipp Gtitlich
Rainer Link
Alfred Trautwein
Mossbauer Spectroscopy and
Transition Metal Chemistry
With 160 Figures
Springer-Verlag
Berlin Heidelberg GmbH 1978
Prof. Dr. Philipp Glitlich
Dr. rer. nat. Rainer Link
Johannes Gutenberg-Universitat
Institut fUr Anorganische und Analytische Chemie
J).6500 Mainz
Prof. Dr. Alfred X. Trautwein
Fachbereich "Angewandte Physik"
der Universitat des Saarlandes
0-6600 Saarbriicken 11
ISBN 978-3-662-12547-2 ISBN 978-3-662-12545-8 (eBook)
DOI 10.1007/978-3-662-12545-8
Library of Congress Cataloging in Publication Data. Giitlich, Philipp, 1934-
Mossbauer spectroscopy and transition metal chemistry. (Inorganic chemistry
concepts; v. 3) Bibliography: p. Includes index. 1. Transition metals-Spectra.
2. Mossbauer spectroscopy. I. Link, Rainer, 1943-joint author. II. Trautwein,
Alfred, 1940-joint author. III. Title. IV. Series. QC462.T86G83 546'.6
78-2364
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© by Springer-Verlag Berlin Heidelberg 1978
Originally published by Springer-Verlag Berlin Heidelberg New York in 1978
Sof'tcover reprint of the hardcover I st edition 1978
The use of registered names, trademarks, etc. in this publication does not imply,
even in the absence of a specific statement, that such names are exempt from
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2152/3140-543210
Preface
Two decades have passed since the original discovery of recoilless
nuclear gamma resonance by Rudolf Mossbauer; the spectroscopic
method based on this resonance effect - referred to as Mossbauer
spectroscopy - has developed into a powerful tool in solid-state
research. The users are chemists, physicists, biologists, geologists,
and scientists from other disciplines, and the spectrum of problems
amenable to this method has become extraordinarily broad.
In the present volume we have confined ourselves to applications
of Mossbauer spectroscopy to the area of transition elements. We
hope that the book will be useful not only to non-Mossbauer special
ists with problem-Oriented activities in the chemistry and physics of
transition elements, but also to those actively working in the field of
Mossbauer spectroscopy on systems (compounds as well as alloys) of
transition elements.
The first five chapters are directed to introducing the reader who
is not familiar with the technique to the principles of the recoilless
nuclear resonance effect, the hyperfme interactions between nuclei
and electronic properties such as electric and magnetic fields, some
essential aspects about measurements, and the evaluation of Moss
bauer spectra. Chapter 6 deals with the interpretation of Mossbauer
parameters of iron compounds. Here we have placed emphasis on the
information about the electronic structure, in correlation with
quantum chemical methods, because of its importance for chemical
bonding and magnetic properties. Some selected references to original
work from the large number of publications on 57Pe Mossbauer spec
troscopy have been cited here; trying to be complete in this instance
was neither our intention in writing this chapter, nor would it have
been possible within the scope of this volume.
In Chapter 7, which deals with Mossbauer active transition elements
other than iron, we have, however, strenuously tried to be complete
as far as the literature is concerned, which deals with investigations of
solid-state problems. It is our hope that this chapter will be particular
ly useful to scientists who are actively concerned with Mossbauer work
on non-iron transition elements.
Chapter 8 finally is intended to give the less informed reader an
impression about the various fields in which the Mossbauer effect
technique has been of great importance. Here again, of course, we
VI Preface
could not refer to all the original work. The many review articles and
other selected papers we have cited here should, however, in our
opinion be well suited to guide the more deeply interested reader into
the relevant literature. The authors wish to express their thanks to the
Deutsche Forschungsgemeinscha/t, the Bundesministerium [iir For
schung und Technologie, and the Fonds der Chemischen Industrie for
the financial support of their research work in the field of Mossbauer
spectroscopy. They also wish to convey their particular thanks to
Professor U. Gonser, Professor F. E. Harris, Professor E. Kankeleit,
and Professor K. H. Lieser for stimulating and fruitful discussions
over many years.
We wish to thank Mrs. G. Lehr and Miss E. Borner for preparing
the manuscript and the many drawings.
Mainz and Saarbrucken, 1978 P. G. R. L. A. T.
Contents
1. Introduction
2. Basic Physical Concepts 4
2.1. Spectral Line Shape and Natural Line Width . 4
2.2. Nuclear Resonance 5
2.3. Recoil Energy Loss, Thennal Broadening of
Transition Lines 6
2.4. The Mossbauer Effect 10
3. Hyperfine Interactions . 13
3.1. Electric Hyperfine Interaction 13
3.1.1. Electric Monopole Interaction; Isomer Shift . 15
3.1.2. Electric Quadrupole Interaction; Quadrupole Splitting 20
3.2. Magnetic Hyperfine Interaction . 26
3.3. Combined Electric and Magnetic Hyperfine
Interactions 28
3.4. Relative Intensities of Resonance Lines 29
3.4.1. Transition Probabilities. 29
3.4.2. Effect of Crystal Anisotropy on the Relative
Intensities of Hyperfme Splitting Components 34
3.5. Experimental Line Shape and Width of Resonant
Absorption 36
4. Experimental 41
4.1. The Mossbauer Spectrometer . 42
4.1.1. General Concept and Mode of Operation 42
4.1.2. Calibration. 44
4.1.3. Detectors 45
4.1.4. Cryostats 48
4.2. Preparation of Mossbauer Sources and Absorbers 48
4.3. Geometrical Considerations 50
s. Mathematical Evaluation of Mossbauer Spectra . 53
VIII Contents
6. Interpretation of Mossbauer Parameters of Iron
Compounds . . . . . 56
6.1. General Aspects . . . . 56
6.2. Molecular Cluster Approach 58
6.3. Electron Densities 60
6.3.1. Ab Initio Calculations . . 60
6.3.2. Approximate MO Calculations 60
6.3.3. Isomer Shift and Electronegativity 66
6.3.4. Second-Order Doppler Shift . . 67
6.4. Quadrupole Splitting . . . . 69
6.4.1. The Electric Field Gradient Tensor . 69
6.4.2. Temperature Independent Quadrupole Splitting 72
6.4.3. Temperature Dependent Quadrupole Splitting 73
6.4.4. Magnetically Induced Quadrupole Splitting 75
6.5. Magnetic Hyperfine Interaction 77
6.5.1. General. . .. . . 77
6.5.2. Example (a-FeS04)' . . . 79
6.5.3. Example (Ferricyanide) 82
6.6. Theoretical Methods for the Description of the
Electronic and Magnetic Structure . . . . . 83
6.7. Fluctuations and Transitions. . . . . . . 84
6.7.1. Simple Example for a Mossbauer Relaxation Spectrum 84
6.7.2. Relaxation Processes 87
6.7.2.1. Spin-Lattice Relaxation 87
6.7.2.2. Spin-Spin Relaxation 95
6.7.2.3. Cross Relaxation. . . 98
6.7.2.4. Superparamagnetism 99
6.7.3. Spin Transitions in Iron Complex Compounds 100
7. Mossbauer-Active Transition Metals Other than Iron 111
7.1. Nickel (61Ni) . . . . . . 113
7.1.1. Some Practical Aspects. . . 113
7.1.2. Hyperfine Interactions in 61Ni 115
7.1.3. Applications . . . . . 122
7.2. Zinc (67Zn) . . . . . 124
7.3. Ruthenium (99Ru, 101Ru) . 130
7.3.1. Experimental Aspects . . 130
7.3.2. Chemical Information from 9~u Mossbauer
Parameters. . . . . . . 132
7.3.3. Further 99Ru Studies . . . . . . . . 141
7.4. Hafnium (176,177,178, 180Hf). . . . . . 142
7.4.1. Practical Aspects of Hafnium Mossbauer Spectroscopy 143
7.4.2. Magnetic Dipole and Electric Quadrupole Hyperfine
Interaction. . . . . . . . . . . . . . . 144
Contents IX
e
7.5. Tantalum 81Ta) 146
7.5.1. Experimental Aspects 148
7.5.2. Isomer Shift Studies 149
7.5.3. Hyperfmee Splitting in 181Ta (6.2 keY) Spectra . 154
7.6. Tungsten 80, 182, 183, 184, 186W) 158
7.6.1. Practical Aspects of Mossbauer Spectroscopy with
Tungsten 159
7.6.2. Chemical Information from Debye-Waller Factor
Measurements . 161
7.6.3. Chemicale Information from Hyperfme Interaction. 163
7.7. Osmium 86, 188, 189, 1900S) . 166
7.7.1. Practical Aspects of Mossbauer Spectroscopy with
Osmium 167
7.7.2. Determination of Nuclear Parameters of Osmium
Mossbauer Isotopes . 170
7.7.3. Inorganiec and Metal Organic Osmium Compounds . 174
7.8. Iridium 91Ir, 193Ir) 177
7.8.1. Practical Aspects of 193Ir (73 keY) Mossbauer
Spectroscopy . 178
7.8.2. Coordination Compounds of Iridium 179
7.8.3. Intermetaellic Compounds and Alloys of Iridium 187
7.9. Platinum 9Spt) . 191
7.9.1. Experimental Aspects 192
7.9.2. Platinum Compounds 193
7.9.3. Metallic Systems . 197
e
7.10. Gold 97Au) 201
7.10.1. Practical Aspects . 202
7.10.2. Inorganic and Metal Organic Compounds of Gold 203
7.10.3. Intermetaellic Compounds and Alloys of Gold 212
7.11. Mercury 99, 201Hg) 218
8. Some Special Applications 223
8.1. Solid-State Reactions 223
8.1.1. Thermal Decomposition 224
8.1.2. Radiolysis Studies 227
8.1.3. Pressure Induced Reactions 228
8.1.4. Ligand Exchange, Electron Transfer, Isomerism 231
8.1.5. Diffusion in Solids and Liquids 233
8.2. Frozen Solution Studies 234
8.3. Surface Studies 237
8.4. Metallurgy . 244
8.4.1. Phases and Transitions 245
8.4.1.1. Interstitial Alloys 245
8.4.1.2. Substitutional Alloys 248
8.4.1.3. Magnetic Properties. 248
X Contents
8.4.1.4. Defects 249
8.4.1.5. Oxidation . . . . 249
8.4.2. Backscatter Technique 249
8.4.3. Further Problems 249
8.5. Aftereffects of Nuclear Transformations 254
8.6. Applications to Biology . . . . . 263
8.6.1. General Significance of Iron in Biology 263
8.6.2. Heme Proteins . . . . . . . . 264
8.6.2.1. Absorption Measurements with Frozen Solutions 264
8.6.2.2. Emission Spectroscopy. . . . . . . . 267
8.6.2.3. Absorption Measurements with Single Crystals 268
8.6.2.4. Scattering Experiments with Single Crystals . 268
8.6.3. Iron Transport and Storage Compounds 271
8.6.3.1. Transferrin. . . 272
8.6.3.2. Ferritin. . . . 273
8.6.4. Enzyme Systems . 273
Subject Index. . . . . . . . . . . . . . . . . 277