Mössbauer Spectroscopy

Principles and Applications

A l f r e d M a d d o c k , BSc, DIC, PhD, ScD(Cantab), DSc(Louvain)

Department of Chemistry
University of Cambridge
and
Fellow of St. Catherine's College

Horwood Publishing
Chichester
 Table of Contents
1 Basis of Mössbauer spectroscopy 1
1.1 Resonance absorption and scattering 1
1.2 Mössbauer effect 3
1.3 Interaction of nucleus with orbital electtons 5
1.4 Interaction with the electric field 6
1.5 Interaction of nucleus with a magnetic field 15
1.6 Combined magnetic and quadrapole interaction 18
2 Practical aspects of Mössbauer spectroscopy 20
2.1 General natureof technique 20
2.2 Sources 20
2.3 Detectors 29
2.4 Doppler modulationof photonenergy 32
2.5 Calibration 36
2.6 Absorbers 37
2.7 Cryostats 41
2.8 Treatmentofdata 42
3 Further consideration of principles 45
3.1 Intensities and angular distributions 45
3.2 Intensities 47
3.3 Angular dependence 49
3.4 Departures from calculated values 51
3.5 The electric field gradient 53
3.6 Temperature dependence of parameters 60
3.7 Sign of the quadrapole Splitting 65
4 Mössbauer spectroscopy in tin chemistry 69
4.1 Spectra of main group elements 69
4.2 Nuclear aspects of119mSn 70
4.3 General features of tin spectra 71
4.4 Isomer shifts intin(IV) spectra 73
4.5 Isomer shifts intin(II) spectra 79
4.6 Quadrapole Splitting in tin Compounds 87
4.7 The recoil free fraction 101
4.8 Spectra in a matrix 101
4.9 Resume of tin studies 103
5 Mössbauer spectroscopy in iron chemistry 104
5:1 Spectroscopy of transition elements 104
5.2 Nuclear considerations with 57Fe 104
5.3 General features of iron spectra 106
5.4 High spin iron Compounds 107
5.5 Low spin iron Compounds 113
5.6 Simple applications of 8 and A 122
5.7 Iron in high oxidation states 130
5.8 Iron in unusual spin states 134
5.9 Five coordinate iron complexes 138
6 Further consideration of magnetic effects 141
6.1 Hyperfine magnetic fields 141
6.2 Ordering in magnetic solids 142
6.3 Relaxation effects 145
6.4 Magnetic spectra from paramagnetic solids 146
6.5 Magnetically ordered Systems 148
6.6 Magnetic dimensionality 152
6.7 Magnetic phase changes 154
7 Further features of iron spectra 159
7.1 Oxides and hydroxides 159
7.2 Spineis and mixed oxides 167
7.3 Low oxidation State Compounds : 174
7.4 Mixed valence Compounds: delocalisation 177
7.5 Spin cross-over 186
7.6 Iron species in Solution, on adsorbents and in matrices 195
8 CEMS and applications in mineralogy and biochemistry 201
8.1 Conversion electron Mössbauer spectroscopy 201
8.2 Reactions inthe solid State 203
8.3 Applications to mineralogy and petrology 205
8.4 Amorphous materials 211
8.5 Applications in biochemistry and medicine 212
8.6 Haem proteins and related Compounds 218
8.7 Iron-sulphur proteins 223
8.8 Protein dynamics 225
8.9 Magnetite and other iron Compounds in organisms 226
8.10 Comments on iron Mössbauer spectroscopy 227
9 Mössbauer spectroscopy of elements other than iron and tin 228
9.1.1 Iodine 228
9.1.2 Antimony 234
9.1.3 Tellurium 236
9.1.4 Xenon 238
9.2.1 Iridium 239
9.2.2 Gold 242
9.2.3 Ruthenium 244
9.2.4 Tungsten 245
9.2.5 Tantalum 246
9.3.1 Europium 247
9.3.2 Neptunium 247
10 Mössbauer emission spectroscopy 251
10.1 Emission spectroscopy 251
10.2 Synthesis inamatrix 252
10.3 Decay involving an Auger cascade 252
10.4 57Co decay in metal halides 254
10.5 Oxide Systems 255
10.6 Implantation Systems 255