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