Gütlich / Bill Mössbauer Spectroscopy and Transition Metal Chemistry

Fundamentals and Applications
1. Auflage 2010
ISBN: 978-3-540-88428-6
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 569 Seiten

concentrates on teaching techniques using as much theory as needed.application of the techniques to many problems of materials characterization.Mössbauer spectroscopy is a profound analytical method which has nevertheless continued to develop. The authors now present a state-of-the art book which consists of two parts. The first part details the fundamentals of Mössbauer spectroscopy and is based on a book published in 1978 in the Springer series 'Inorganic Chemistry Concepts' by P. Gütlich, R. Link and A.X. Trautwein. The second part covers useful practical aspects of measurements, and the application of the techniques to many problems of materials characterization. The update includes the use of synchroton radiation and many instructive and illustrative examples in fields such as solid state chemistry, biology and physics, materials and the geosciences, as well as industrial applications.  Special chapters on magnetic relaxation phenomena (S. Morup) and computation of hyperfine interaction parameters (F. Neese) are also included. The book concentrates on teaching the technique using theory as much as needed and as little as possible. The reader will learn the fundamentals of the technique and how to apply it to many problems of materials characterization. Transition metal chemistry, studied on the basis of the most widely used Mössbauer isotopes, will be in the foreground.

Autoren/Hrsg.

Gütlich, Philipp

Bill, Eckhard

Inhaltsverzeichnis

1;Mössbauer Spectroscopy and Transition Metal Chemistry;3
1.1;Fundamentals and Applications;3
1.2;Preface;5
1.3;Contents;9
1.4;Chapter 1: Introduction;17
1.4.1;References;19
1.5;Chapter 2: Basic Physical Concepts;22
1.5.1;2.1 Nuclear gamma-Resonance;22
1.5.2;2.2 Natural Line Width and Spectral Line Shape;24
1.5.3;2.3 Recoil Energy Loss in Free Atoms and Thermal Broadening of Transition Lines;25
1.5.4;2.4 Recoil-Free Emission and Absorption;28
1.5.5;2.5 The Mössbauer Experiment;32
1.5.6;2.6 The Mössbauer Transmission Spectrum;33
1.5.6.1;2.6.1 The Line Shape for Thin Absorbers;36
1.5.6.2;2.6.2 Saturation for Thick Absorbers;38
1.5.7;References;39
1.6;Chapter 3: Experimental;40
1.6.1;3.1 The Mössbauer Spectrometer;40
1.6.1.1;3.1.1 The Mössbauer Drive System;42
1.6.1.1.1;3.1.1.1 Setup and Function;42
1.6.1.1.2;3.1.1.2 Tuning the Drive Performance;43
1.6.1.2;3.1.2 Recording the Mössbauer Spectrum;44
1.6.1.2.1;3.1.2.1 ``Folding´´ of Raw Spectra;45
1.6.1.3;3.1.3 Velocity Calibration;46
1.6.1.3.1;3.1.3.1 Velocity Range and Calibration Factor;46
1.6.1.3.2;3.1.3.2 Velocity Zero and Isomer Shift References;47
1.6.1.3.3;3.1.3.3 Laser Calibration;48
1.6.1.4;3.1.4 The Mössbauer Light Source;49
1.6.1.5;3.1.5 Pulse Height Analysis: Discrimination of Photons;50
1.6.1.5.1;3.1.5.1 Tuning the SCA;51
1.6.1.6;3.1.6 Mössbauer Detectors;52
1.6.1.6.1;3.1.6.1 Proportional Counters;52
1.6.1.6.2;3.1.6.2 Other gamma-Detectors;53
1.6.1.6.3;3.1.6.3 Detectors for Conversion Electrons and Scattered Radiation;54
1.6.1.6.4;3.1.6.4 Limits of Counter Resolution;56
1.6.1.7;3.1.7 Accessory Cryostats and Magnets;56
1.6.1.8;3.1.8 Geometry Effects and Source-Absorber Distance;58
1.6.2;3.2 Preparation of Mössbauer Sources and Absorbers;60
1.6.2.1;3.2.1 Sample Preparation;61
1.6.2.1.1;3.2.1.1 Basic Considerations;61
1.6.2.1.2;3.2.1.2 Counting Statistics and Acquisition Time;62
1.6.2.1.3;3.2.1.3 Minimal Thickness of a Mössbauer Sample;63
1.6.2.2;3.2.2 Absorber Optimization: Mass Absorption and Thickness;64
1.6.2.2.1;3.2.2.1 Mass Absorption Coefficients;65
1.6.2.2.2;3.2.2.2 Solvents, Solutions, and Powders;66
1.6.2.2.3;3.2.2.3 Isotope Enrichment;67
1.6.2.3;3.2.3 Absorber Temperature;67
1.6.3;3.3 The Miniaturized Spectrometer MIMOS II;68
1.6.3.1;3.3.1 Introduction;68
1.6.3.2;3.3.2 Design Overview;69
1.6.3.2.1;3.3.2.1 Mössbauer Sources, Shielding, and Collimator;70
1.6.3.2.2;3.3.2.2 Drive System;72
1.6.3.2.3;3.3.2.3 Detector System and Electronics;73
1.6.3.3;3.3.3 Backscatter Measurement Geometry;74
1.6.3.3.1;3.3.3.1 Cosine Smearing;75
1.6.3.4;3.3.4 Temperature Dependence and Sampling Depth;77
1.6.3.4.1;3.3.4.1 Temperature Dependence;77
1.6.3.4.2;3.3.4.2 Sampling Depth;78
1.6.3.5;3.3.5 Data Structure, Temperature Log, and Backup Strategy;80
1.6.3.6;3.3.6 Velocity and Energy Calibration;81
1.6.3.6.1;3.3.6.1 Velocity Calibration;81
1.6.3.6.2;3.3.6.2 Detector Calibration;82
1.6.3.7;3.3.7 The Advanced Instrument MIMOS IIa;82
1.6.4;References;84
1.7;Chapter 4: Hyperfine Interactions;87
1.7.1;4.1 Introduction to Electric Hyperfine Interactions;87
1.7.1.1;4.1.1 Nuclear Moments;89
1.7.1.2;4.1.2 Electric Monopole Interaction;89
1.7.1.3;4.1.3 Electric Quadrupole Interaction;90
1.7.1.4;4.1.4 Quantum Mechanical Formalism for the Quadrupole Interaction;91
1.7.2;4.2 Mössbauer Isomer Shift;93
1.7.2.1;4.2.1 Relativistic Effects;95
1.7.2.2;4.2.2 Isomer Shift Reference Scale;95
1.7.2.3;4.2.3 Second-Order Doppler Shift;95
1.7.2.4;4.2.4 Chemical Information from Isomer Shifts;97
1.7.2.4.1;4.2.4.1 Isomer Shift Correlations;97
1.7.2.4.2;4.2.4.2 Oxidation State and Spin;98
1.7.2.4.3;4.2.4.3 Applications of Isomer Shift Correlations;100
1.7.2.4.4;4.2.4.4 Covalent Bonding Properties;100
1.7.2.4.5;4.2.4.5 Basic Interpretation;101
1.7.3;4.3 Electric Quadrupole Interaction;103
1.7.3.1;4.3.1 Nuclear Quadrupole Moment;104
1.7.3.2;4.3.2 Electric Field Gradient;104
1.7.3.3;4.3.3 Quadrupole Splitting;106
1.7.3.4;4.3.4 Interpretation and Computation of Electric Field Gradients;109
1.7.3.4.1;4.3.4.1 EFG from Point Charges;109
1.7.3.4.2;4.3.4.2 The ``Lattice Contribution´´ to the EFG;111
1.7.3.4.3;4.3.4.3 Local Contribution from Valence Electrons;112
1.7.4;4.4 Magnetic Dipole Interaction and Magnetic Splitting;116
1.7.5;4.5 Combined Electric and Magnetic Hyperfine Interactions;117
1.7.5.1;4.5.1 Perturbation Treatment;118
1.7.5.2;4.5.2 High-Field Condition: gNNBeQVzz/2;118
1.7.5.2.1;4.5.2.1 Quadrupole Shifts in High-Field Magnetic Spectra;120
1.7.5.2.2;4.5.2.2 Angular Dependence of the Effect of Quadrupole Interaction in High-Field Spectra;120
1.7.5.3;4.5.3 Low-Field Condition: eQVzz/2gNNB;122
1.7.5.4;4.5.4 Effective Nuclear g-Factors for eQVzz/2gNNB;125
1.7.5.5;4.5.5 Remarks on Low-Field and High-Field Mössbauer Spectra;126
1.7.6;4.6 Relative Intensities of Resonance Lines;127
1.7.6.1;4.6.1 Transition Probabilities;127
1.7.6.2;4.6.2 Effect of Crystal Anisotropy on the Relative Intensities of Hyperfine Splitting Components;132
1.7.7;4.7 57Fe-Mössbauer Spectroscopy of Paramagnetic Systems;134
1.7.7.1;4.7.1 The Spin-Hamiltonian Concept;135
1.7.7.1.1;4.7.1.1 Ground State Properties and Zero-Field Splitting;136
1.7.7.2;4.7.2 The Formalism for Electronic Spins;138
1.7.7.3;4.7.3 Nuclear Hamiltonian and Hyperfine Coupling;139
1.7.7.3.1;4.7.3.1 Separation of I- and S-Dependent Contributions;140
1.7.7.4;4.7.4 Computation of Mössbauer Spectra in Slow and Fast Relaxation Limit;141
1.7.7.5;4.7.5 Spin Coupling;142
1.7.7.6;4.7.6 Interpretation, Remarks and Relation with Other Techniques;145
1.7.8;References;146
1.8;Chapter 5: Quantum Chemistry and Mössbauer Spectroscopy;150
1.8.1;5.1 Introduction;150
1.8.2;5.2 Electronic Structure Theory;151
1.8.2.1;5.2.1 The Molecular Schrdinger Equation;151
1.8.2.2;5.2.2 Hartree-Fock Theory;152
1.8.2.3;5.2.3 Spin-Polarization and Total Spin;155
1.8.2.4;5.2.4 Electron Density and Spin-Density;157
1.8.2.5;5.2.5 Post-Hartree-Fock Theory;158
1.8.2.6;5.2.6 Density Functional Theory;159
1.8.2.7;5.2.7 Relativistic Effects;161
1.8.2.8;5.2.8 Linear Response and Molecular Properties;162
1.8.3;5.3 Mössbauer Properties from Density Functional Theory;163
1.8.3.1;5.3.1 Isomer Shifts;163
1.8.3.1.1;5.3.1.1 Calibration Approach;163
1.8.3.1.2;5.3.1.2 An Example;164
1.8.3.1.3;5.3.1.3 Advanced Considerations;166
1.8.3.1.4;5.3.1.4 Linear Response Treatment;173
1.8.3.1.5;5.3.1.5 Solid State and Semiempirical Methods;174
1.8.3.1.6;5.3.1.6 Interpretation of the Isomer Shift;175
1.8.3.2;5.3.2 Quadrupole Splittings;177
1.8.3.2.1;5.3.2.1 Correlation with Experiment;178
1.8.3.2.2;5.3.2.2 Physical Interpretation of the Electric Field Gradient Tensor;179
1.8.3.2.2.1;One Center Contributions;180
1.8.3.2.2.2;One-Center Core Polarization;180
1.8.3.2.2.3;One Center Valence Contributions;181
1.8.3.2.2.4;Two Center Point-Charge Contributions;183
1.8.3.2.2.5;Two-Center-Bond Contributions;185
1.8.3.2.2.6;Three Center Contributions;185
1.8.3.2.3;5.3.2.3 An Example;185
1.8.3.2.4;5.3.2.4 Temperature-Dependent Quadrupole Splitting;188
1.8.3.3;5.3.3 Magnetic Hyperfine Interaction;191
1.8.3.3.1;5.3.3.1 Theory;191
1.8.3.3.2;5.3.3.2 Correlation with Experiment;191
1.8.3.3.2.1;Isotropic Magnetic Hyperfine Couplings;191
1.8.3.3.2.2;Anisotropic Hyperfine Interaction;193
1.8.3.3.3;5.3.3.3 Problems with Density Functional Theory;193
1.8.3.3.4;5.3.3.4 Physical Interpretation;193
1.8.3.3.4.1;Isotropic Magnetic Hyperfine Interaction;193
1.8.3.3.4.2;Dipolar Magnetic Hyperfine Interaction;196
1.8.3.3.4.3;Spin-Orbit Coupling Contribution to the Magnetic HFC;196
1.8.3.3.5;5.3.3.5 An Example;197
1.8.3.4;5.3.4 Zero-Field Splitting and g-Tensors;198
1.8.4;5.4 Nuclear Inelastic Scattering;199
1.8.4.1;5.4.1 The NIS Intensity;200
1.8.4.2;5.4.2 Example 1: NIS Studies of an Fe(III)-azide(Cyclam-acetato) Complex;202
1.8.4.2.1;5.4.2.1 Normal Mode Compositions;205
1.8.4.3;5.4.3 Example 2: Quantitative Vibrational Dynamics of Iron Ferrous Nitrosyl Tetraphenylporphyrin;206
1.8.5;References;209
1.9;Chapter 6: Magnetic Relaxation Phenomena;213
1.9.1;6.1 Introduction;213
1.9.2;6.2 Mössbauer Spectra of Samples with Slow Paramagnetic Relaxation;214
1.9.3;6.3 Mössbauer Relaxation Spectra;217
1.9.4;6.4 Paramagnetic Relaxation Processes;222
1.9.4.1;6.4.1 Spin-Lattice Relaxation;223
1.9.4.2;6.4.2 Spin-Spin Relaxation;226
1.9.5;6.5 Relaxation in Magnetic Nanoparticles;232
1.9.5.1;6.5.1 Superparamagnetic Relaxation;232
1.9.5.2;6.5.2 Collective Magnetic Excitations;235
1.9.5.3;6.5.3 Interparticle Interactions;238
1.9.6;6.6 Transverse Relaxation in Canted Spin Structures;241
1.9.7;References;244
1.10;Chapter 7: Mössbauer-Active Transition Metals Other than Iron;247
1.10.1;7.1 Nickel (61Ni);249
1.10.1.1;7.1.1 Some Practical Aspects;249
1.10.1.2;7.1.2 Hyperfine Interactions in 61Ni;250
1.10.1.2.1;7.1.2.1 Isomer Shifts;250
1.10.1.2.2;7.1.2.2 Magnetic Interactions;253
1.10.1.2.3;7.1.2.3 Electric Quadrupole Interactions;254
1.10.1.2.4;7.1.2.4 Combined Magnetic and Quadrupole Interactions;257
1.10.1.3;7.1.3 Selected 61Ni Mssbauer Effect Studies;258
1.10.2;7.2 Zinc (67Zn);267
1.10.2.1;7.2.1 Experimental Aspects;267
1.10.2.2;7.2.2 Selected 67Zn Mssbauer Effect Studies;274
1.10.2.2.1;7.2.2.1 Gravitational Red Shift Experiments;274
1.10.2.2.2;7.2.2.2 Zinc Metal and Alloys;274
1.10.2.2.3;7.2.2.3 Inorganic Zinc Compounds;276
1.10.2.2.4;7.2.2.4 67Zn Mössbauer Emission Spectroscopy;279
1.10.3;7.3 Ruthenium (99Ru, 101Ru);282
1.10.3.1;7.3.1 Experimental Aspects;282
1.10.3.2;7.3.2 Chemical Information from 99Ru Mssbauer Parameters;282
1.10.3.2.1;7.3.2.1 Isomer Shift;284
1.10.3.2.2;7.3.2.2 Quadrupole Splitting;289
1.10.3.2.3;7.3.2.3 Magnetic Splitting;293
1.10.3.3;7.3.3 Further 99Ru Studies;296
1.10.4;7.4 Hafnium (176,177,178,180Hf);297
1.10.4.1;7.4.1 Practical Aspects of Hafnium Mssbauer Spectroscopy;298
1.10.4.2;7.4.2 Magnetic Dipole and Electric Quadrupole Interaction;300
1.10.5;7.5 Tantalum (181Ta);301
1.10.5.1;7.5.1 Experimental Aspects;302
1.10.5.2;7.5.2 Isomer Shift Studies;304
1.10.5.3;7.5.3 Hyperfine Splitting in 181Ta (6.2keV) Spectra;308
1.10.5.3.1;7.5.3.1 Quadrupole Splitting;308
1.10.5.3.2;7.5.3.2 Magnetic Dipole Splitting;310
1.10.5.4;7.5.4 Methodological Advances and Selected Applications;312
1.10.6;7.6 Tungsten (180,182,183,184,186W);313
1.10.6.1;7.6.1 Practical Aspects of Mössbauer Spectroscopy with Tungsten;315
1.10.6.2;7.6.2 Chemical Information from Debye-Waller Factor Measurements;317
1.10.6.3;7.6.3 Chemical Information from Hyperfine Interaction;318
1.10.6.4;7.6.4 Further 183W Studies;321
1.10.7;7.7 Osmium (186,188,189,190Os);322
1.10.7.1;7.7.1 Practical Aspects of Mössbauer Spectroscopy with Osmium;323
1.10.7.2;7.7.2 Determination of Nuclear Parameters of Osmium Mössbauer Isotopes;325
1.10.7.2.1;7.7.2.1 Magnetic Moments and E2/M1 Mixing Parameter;325
1.10.7.2.2;7.7.2.2 Nuclear Quadrupole Moments;327
1.10.7.2.3;7.7.2.3 Change of Nuclear Charge Radii;327
1.10.7.3;7.7.3 Inorganic Osmium Compounds;329
1.10.8;7.8 Iridium (191,193Ir);332
1.10.8.1;7.8.1 Practical Aspects of 193Ir Mssbauer Spectroscopy;333
1.10.8.2;7.8.2 Coordination Compounds of Iridium;334
1.10.8.3;7.8.3 Intermetallic Compounds and Alloys of Iridium;341
1.10.8.4;7.8.4 Recent 193Ir Mssbauer Studies;349
1.10.9;7.9 Platinum (195Pt);351
1.10.9.1;7.9.1 Experimental Aspects;351
1.10.9.2;7.9.2 Platinum Compounds;353
1.10.9.3;7.9.3 Metallic Systems;356
1.10.10;7.10 Gold (197Au);360
1.10.10.1;7.10.1 Practical Aspects;361
1.10.10.2;7.10.2 Inorganic and Metal-Organic Compounds of Gold;362
1.10.10.3;7.10.3 Specific Applications;373
1.10.10.3.1;7.10.3.1 Gold in Medicine;373
1.10.10.3.2;7.10.3.2 Gold Substitution in High-Tc Superconductors;373
1.10.10.3.3;7.10.3.3 Gold Minerals and Ores;374
1.10.10.3.4;7.10.3.4 Gold-Containing Catalysts;375
1.10.10.3.5;7.10.3.5 Gold Clusters;376
1.10.10.3.6;7.10.3.6 Gold Multilayers;377
1.10.10.3.7;7.10.3.7 Intermetallic Compounds;378
1.10.10.3.8;7.10.3.8 Alloys;381
1.10.11;7.11 Mercury (199,201Hg);385
1.10.12;References;388
1.10.13;References to Sect. 7.1;388
1.10.14;References to Sect. 7.2;389
1.10.15;References to Sect. 7.3;391
1.10.16;References to Sect. 7.4;393
1.10.17;References to Sect. 7.5;393
1.10.18;References to Sect. 7.6;395
1.10.19;References to Sect. 7.7;396
1.10.20;References to Sect. 7.8;396
1.10.21;References to Sect. 7.9;397
1.10.22;References to Sect. 7.10;398
1.10.23;References to Sect. 7.11;402
1.11;Chapter 8: Some Special Applications;403
1.11.1;8.1 Spin Crossover Phenomena in Fe(II) Complexes;404
1.11.1.1;8.1.1 Introduction;404
1.11.1.2;8.1.2 Spin Crossover in [Fe(2-pic)3]Cl2cSol;408
1.11.1.3;8.1.3 Effect of Light Irradiation (LIESST Effect);411
1.11.1.4;8.1.4 Spin Crossover in Dinuclear Iron(II) Complexes;415
1.11.1.5;8.1.5 Spin Crossover in a Trinuclear Iron(II) Complex;420
1.11.1.6;8.1.6 Spin Crossover in Metallomesogens;423
1.11.1.7;8.1.7 Effect of Nuclear Decay: Mössbauer Emission Spectroscopy;425
1.11.2;8.2 57Fe Mössbauer Spectroscopy: Unusual Spin and Valence States;429
1.11.2.1;8.2.1 Iron(III) with Intermediate Spin, S=3/2;429
1.11.2.1.1;8.2.1.1 Ligand Field Considerations;429
1.11.2.1.2;8.2.1.2 Mössbauer Parameters;430
1.11.2.1.2.1;Square- and Rhombic-Pyramidal Complexes;431
1.11.2.1.2.1.1;S4X Ligand Sphere;431
1.11.2.1.2.1.2;S2N2X Ligand Sphere;433
1.11.2.1.2.1.3;O2N2X Ligand Sphere;433
1.11.2.1.2.1.4;N4X Ligand Sphere;434
1.11.2.1.2.2;Six-Coordinate Complexes;434
1.11.2.1.2.3;Common Features and Electronic Structures;435
1.11.2.1.3;8.2.1.3 Spin Admixture S=(5/2, 3/2) in Porphyrinates: A Special Case?;436
1.11.2.2;8.2.2 Iron(II) with Intermediate Spin, S=1;437
1.11.2.2.1;8.2.2.1 Square-Planar Iron(II) Compounds;437
1.11.2.2.1.1;Six-Coordinate Iron(II) Complexes;440
1.11.2.3;8.2.3 Iron in the High Oxidation States IV-VI;440
1.11.2.3.1;8.2.3.1 Crystal-Field Ground States;441
1.11.2.3.2;8.2.3.2 Iron(IV) Oxides;442
1.11.2.3.3;8.2.3.3 Iron(IV) in Metalloproteins and Coordination Compounds;442
1.11.2.3.3.1;Heme Iron(IV) Oxo Centers;444
1.11.2.3.3.2;Nonheme Iron(IV) Oxo Centers;445
1.11.2.3.3.3;High-Valent Iron Dimers;446
1.11.2.3.3.4;Mononuclear Iron(IV)-Nitrido and -Imido Compounds;447
1.11.2.3.3.5;Nonoxo-, Nonnitrido-Iron(IV) Compounds;448
1.11.2.3.3.6;Corroles and Other Noninnocent Ligands;449
1.11.2.3.4;8.2.3.4 Iron(V) Compounds;450
1.11.2.3.5;8.2.3.5 Iron(VI) Compounds;451
1.11.2.4;8.2.4 Iron in Low Oxidation States;452
1.11.2.4.1;8.2.4.1 Low-Valent Iron Porphyrins;453
1.11.2.4.2;8.2.4.2 Three- and Four-Coordinate Low-Valent Iron Compounds;455
1.11.2.4.3;8.2.4.3 Low-Spin Iron in the Active Site of Hydrogenases;456
1.11.2.4.3.1;[FeFe]-Hydrogenases;456
1.11.2.4.3.2;[NiFe]-Hydrogenases;457
1.11.2.4.3.3;[Fe]-Hydrogenase;457
1.11.3;8.3 Mobile Mössbauer Spectroscopy with MIMOS in Space and on Earth;459
1.11.3.1;8.3.1 Introduction;459
1.11.3.2;8.3.2 The Instrument MIMOS II;460
1.11.3.3;8.3.3 Examples;463
1.11.3.3.1;8.3.3.1 Mars-Exploration-Rover Mission;463
1.11.3.3.2;8.3.3.2 Terrestrial Applications;471
1.11.3.3.3;8.3.3.3 The Advanced Instrument MIMOS IIa;475
1.11.3.4;8.3.4 Conclusions and Outlook;476
1.11.4;References;476
1.11.5;References to Sect. 8.1;395
1.11.6;References to Sect. 8.2;393
1.11.7;References to Sect. 8.3;391
1.12;Chapter 9: Nuclear Resonance Scattering Using Synchrotron Radiation (Mössbauer Spectroscopy in the Time Domain);489
1.12.1;9.1 Introduction;489
1.12.2;9.2 Instrumentation;490
1.12.3;9.3 Nuclear Forward Scattering (NFS);491
1.12.3.1;9.3.1 Quadrupole Splitting: Theoretical Background;492
1.12.3.2;9.3.2 Effective Thickness, Lamb-Mössbauer Factor;492
1.12.4;9.4 NFS Applications;495
1.12.4.1;9.4.1 Polycrystalline Material Versus Frozen Solution (Example: ``Picket-Fence´´ Porphyrin and Deoxymyoglobin);495
1.12.4.2;9.4.2 Temperature-Dependent Quadrupole Splitting in Paramagnetic (S=2) Iron Compounds (Example: Deoxymyoglobin);498
1.12.4.3;9.4.3 Dynamically Induced Temperature-Dependence of Quadrupole Splitting (Example: Oxymyoglobin);499
1.12.4.4;9.4.4 Molecular Dynamics of a Sensor Molecule in Various Hosts (Example: Ferrocene (FC));502
1.12.4.5;9.4.5 Temperature-Dependent Quadrupole Splitting and Lamb-Mössbauer Factor in Spin-Crossover Compounds(Example: [FeII(tpa)(NCS)2]);503
1.12.4.6;9.4.6 Coherent Versus Incoherent Superposition of Forward Scattered Radiation of High-Spin and Low-Spin Domains (Example: [FeII(tpa)(NCS)2]);505
1.12.4.7;9.4.7 Orientation-Dependent Line-Intensity Ratio and Lamb-Mössbauer Factor in Single Crystals (Example: (CN3H6)2[Fe(CN)5NO]);507
1.12.5;9.5 Isomer Shift Derived from NFS (Including a Reference Scatterer);509
1.12.6;9.6 Magnetic Interaction Visualized by NFS;510
1.12.6.1;9.6.1 Magnetic Interaction in a Diamagnetic Iron Complex (Example: [FeO2(SC6HF4)(TPpivP)]);510
1.12.6.2;9.6.2 Magnetic Hyperfine Interaction in Paramagnetic Iron Complexes (Examples: [Fe(CH3COO)(TPpivP)]- with S=2 and [TPPFe(NH2PzH)2]Cl with S = 1/2);510
1.12.6.3;9.6.3 Magnetic Hyperfine Interaction and Spin-Lattice Relaxation in Paramagnetic Iron Complexes (Examples: Ferric Low-Spin (FeII, S=2));515
1.12.6.4;9.6.4 Superparamagnetic Relaxation (Example: Ferritin);517
1.12.6.5;9.6.5 High-Pressure Investigations of Magnetic Properties (Examples: Laves Phases and Iron Oxides);520
1.12.7;9.7 NFS Visualized by the Nuclear Lighthouse Effect (NLE) (Example: Iron Foil);523
1.12.8;9.8 Synchrotron Radiation Based Perturbed Angular Correlation, SRPAC (Example: Whole-Molecule Rotation of FC);524
1.12.9;9.9 Nuclear Inelastic Scattering;528
1.12.9.1;9.9.1 Phonon Creation and Annihilation;528
1.12.9.2;9.9.2 Data Analysis and DOS (Example: Hexacyanoferrate);530
1.12.9.3;9.9.3 Data Analysis Using Absorption Probability Density (Example: Guanidinium Nitroprusside);532
1.12.9.4;9.9.4 Iron-Ligand Vibrations in Spin-Crossover Complexes;535
1.12.9.4.1;9.9.4.1 Thermally Induced Spin Transition (Example: [Fe(tpa)(NCS)2]);535
1.12.9.4.2;9.9.4.2 Entropy Change Upon Transition (Example: [Fe(Phen)2(NCS)2]);538
1.12.9.5;9.9.5 Boson Peak, a Signature of Delocalized Collective Motions in Glasses (Example: FC as Sensor Molecule);538
1.12.9.6;9.9.6 Protein Dynamics Visualized by NIS;540
1.12.9.6.1;9.9.6.1 Iron-Sulfur Proteins (Examples: FeS4 - and Fe4S4 - Centers);541
1.12.9.6.2;9.9.6.2 Heme Proteins (Examples: Deoxy-, CO- and Metmyoglobin);544
1.12.10;9.10 Nuclear Resonance Scattering with Isotopes Other Than 57Fe;546
1.12.11;References;548
1.13;Chapter 10: Appendices;552
1.13.1;Appendix A: Optimization of Sample Thickness;552
1.13.1.1;References;553
1.13.2;Appendix B: Mass Absorption Coefficients;554
1.13.3;Appendix C: The Isomer Shift Calibration Constant;555
1.13.3.1;References;556
1.13.4;Appendix D: Relativistic Corrections for the Mössbauer Isomer Shift;557
1.13.4.1;References;557
1.13.5;Appendix E: An Introduction to Second-Order Doppler Shift;558
1.13.5.1;References;559
1.13.6;Appendix F: Formal and Spectroscopic Oxidation States;560
1.13.6.1;References;561
1.13.7;Appendix G: Spin-Hamiltonian Operator with Terms of Higher Order in S;561
1.13.7.1;References;562
1.13.8;Appendix H: Remark on Spin-Lattice Relaxation;562
1.13.9;References;563
1.13.10;Appendix I: Physical Constants and Conversion Factors;564
1.13.10.1;References;567
1.14;Index;568