Mössbauer Spectroscopy Applied to Inorganic Chemistry

Transcription

1 Mössbauer Spectroscopy Applied to Inorganic Chemistry Volume 2 Edited by Gary J. Long University of Missouri Rolla Rolla, Missouri \ PLENUM PRESS NEW YORK AND LONDON

2 Chapter 1. Ion Implantation Mössbauer Effect Studies H. de Waard and L. Niesen 1. Introduction 1 2. The Ion Implantation Process Energy Loss and Range of Implanted Ions Radiation Damage Distribution Microscopic Description of the Damage Cascade Final Site of Implanted Impurities Recovery Phenomena 8 3. Ion Implantation Techniques Isotope Separators Recoil Implantation Implantation in Metals Magnetic Hyperfine Fields of Impurities in Ferromagnetic Metals Crystalline Electric Field on Rare Earth Impurities Trapping of Intrinsic Point Defects Clus\ers of Impurities and Light Interstitial Atoms Aggregation Phenomena in Implanted Metals Implantation-Induced Structural Changes Implantation into Semiconductors Introduction to Annealing Techniques Tetravalent Semiconductors III-V Compound Semiconductors II-VI Compound Semiconductors Implantation into Insulators Implantation Studies in Diamond and Graphite Studies of Implantation in Chemical Compounds Implantation in Frozen Gases and Liquids Conclusions 79 Ref erences 80 IX

3 x Chapter 2. Contents Mössbauer Effect Studies of Microcrystalline Materials Steen M0rup 1. Introduction Magnetic Properties of Microcrystals Single-Domain Particles Superparamagnetic Relaxation Collective Magnetic Excitations Applied Magnetic Fields Superferromagnetism Surface Effects Applications Biology Catalysis ( Ferrofluids Terrestrial and Extraterrestrial Minerals Magnetic Tapes Conclusions 119 References 119 Chapter 3. Mössbauer Spectroscopy of Mixed-Valence Compounds Hellmut Eckert 1. Introduction General Principles of Mössbauer Spectroscopy in Mixed- Valence Compounds Valence Fluctuations in Intermetallic Compounds and Related Systems Zero Interconfigurational Excitation Energies: Mixed-Valence Samarium Compounds Finite Interconfigurational Excitation Energies: Mixed-Valence Europium Compounds Mixed-Valence Oxide Systems Simple Binary and Ternary Oxides Magnetite, Fe Cation Distribution and Charge Relaxation in Spineis High Mixed-Valence Oxidation States in Perovskite Phases Charge Transfer in Intercalation Compounds Silicate, Borate, and Phosphate Minerals The Fe(III):Fe(II) Ratio Valence Distribution Studies 160

4 xi 5.3. Electron Exchange Properties Borate and Phosphate Systems Halide Systems Simple Binary and Ternary Metal Halides Metal Halide Intercalation Compounds Iodine Charge Transfer Complexes, Polyiodides, and Iodine-Doped Conducting Polymers Sulfides: Covalent Effects in Mixed-Valence Compounds Ionic Mixed-Valence Sulfides Covalent Sulfides with Intermediate Valences Molecular Systems Compounds with Unknown Molecular Structures Valence States in Iron and Ruthenium Cyanides and Related Systems Dynamic Disorder and Electron Transfer in Trinuclear Iron Acetate Complexes ; Organometallic Systems Conclusions 194 References 195 Chapter 4. Mössbauer Effect Studies on Low-Dimensional Magnetic Solids M.F. Thomas 1. Introduction Magnetic Dimensionality Magnetic Anisotropy Spin Fluctuations in Antiferromagnets Spin Fluctuations and Hyperfine Field Effect of Applied Field on Hyperfine Field Effect of Applied Field on Neel Temperature Magnetic Ordering Effect of Dimensionality and Anisotropy on the Existence of an Ordered Magnetic Phase A Mössbauer Investigation of Ordering in Quasi-Two-Dimensional Heisenberg Systems Critical Fluctuations Nonlinear Excitations in One-Dimensional Magnetic Systems Linear and Nonlinear Excitations Observation of Nonlinear Excitations in Mössbauer Spectra 233

5 xü Contents 4.3. A Study of Nonlinear Excitations in RbFeCl 3-2H Conclusions 239 References 239 Chapter 5. Chemical Influences on the Supertransferred Hyperfine Field Fernande Grandjean 1. Introduction Theoretical Background _^ Experimental Results Ionic Compounds Semimetallic Compounds Conclusions 270 References 271 Chapter 6. Mössbauer Spectroscopy of Reduced Ferritin R.B. Frankel, G.C. Papaefthymiou, and G.D. Watt 1. Introduction Mössbauer Spectroscopy of Oxidized Ferritin Reduction of Ferritin Mössbauer Spectroscopy of Reduced Ferritin Binding of Fe 2+ by Ferritin Conclusions 284 References 287 Chapter 7. Mössbauer Effect Studies of Metallic Glasses Geoffrey Longworth 1. Introduction Historical Background Definition and Classification of Metallic Glasses Methods of Preparation Properties and Uses Analysis of Spectra Survey of Methods Use of Discrete Hyperfine Fields Use of Analytical Functions Use of Fourier Techniques Use of Step Functions 298

6 xiii 3.6. Influence of Magnetic Texture Range of Validity of P(H) Calculations Correlations between Hyperfine Parameters Distribution of Quadrupole Splittings Mössbauer Measurements in Metal-Metalloid Glasses Shape of P(H) Distribution Temperature Variation of Hyperfine Field Magnetic Ordering Magnetic Texture Crystallization Local Structure Mössbauer Measurements in Metal-Metal Glasses Isomer Shifts Magnetic Properties Iron-Zirconium Glasses Hydrogenation of Metallic Glasses Magnetic Structures in Metallic Glasses Magnetic Properties of Fe-Y Glasses Magnetic Structures in Dy-TM Glasses Magnetic Structures in Amorphous Europium Alloys Summary 335 Ref erences 337 Chapter 8. Tellurium-125 Mössbauer Spectroscopy in the Characterization of Tellurium Compounds Frank J. Berry 1. Introduction Tellurium-125 Mössbauer Spectroscopy Sources Detectors Other Considerations Metallic Phases and Inorganic Tellurides Tellurium Inorganic Tellurides Inorganic Compounds Halides Oxides and Related Compounds Organic Compounds Organic Tellurides and Ditellurides Organotellurium(IV) Halides 364

7 xiv Contents 5.3. Additivity Model for the Quadrupole Splittings Heterocyclic Tellurium Compounds Other Compounds Tellurium Ligands Compounds with Tellurium to Metal Bonds Tellurium-Containing Charge Transfer Complexes Tellurium Complexes with Thiourea and Related Compounds Iodine-125 Emission Mössbauer Studies Conclusions 385 References 386 Chapter 9. Mössbauer Spectroscopy with the lodine Isotopes R.V. Parish 1. Introduction Interpretation of Data Brief Overview of Data IonicHalides Covalent Iodides Two-Coordinate Iodine(I) Polyiodides The Di-and Tetraiodine Cations Iodine(III) Iodine(V) Conclusions 424 References 425 Chapter 10. Mössbauer Spectroscopic Studies of Compounds of the 5d Transition Metals Alan F. Williams 1. Introduction Nuclear Properties and Practical Details Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury 442

8 xv Summary Trends in Hyperfine Interactions IsomerShifts Quadrupole Coupling Survey of Results for Individual Elements Hafnium Compounds Tantalum Compounds Tungsten Compounds Osmium Compounds Iridium Compounds Platinum Compounds Gold Compounds Mercury Compounds Conclusions 474 References 475 Chapter 11. Mössbauer Effect Studies of the Actinides B.D. Dunlap 1. Introduction Methodology Hyperfine Parameters Halides Actinyl Compounds Organometallics Chalcogenides Oxides Conclusions 503 References 504 Chapter 12. Iron Oxides and Oxyhydroxides Enver Murad and James H. Johnston 1. Introduction Structures, Magnetic Properties, and Mössbauer Spectra of Individual Oxides Stoichiometric Spineis Nonstoichiometric Iron Oxides Rhombohedral Iron Oxides FeOOH Polymorphs Ferrihydrite Hydrolysis Polymers GreenRust 550

9 3. Applications Iron Oxides in the Marine and Limnic Environments Soils Meteorites Anthropogenic Artifacts 570 References 574 Author Index 583 Subj ect Index 601