Moessbauer spectroscopy

Rudolph Mossbauer discovered the phenomenon of recoil-free nuclear resonance fluorescence in 1957-58 and the first indications of hyperfine interactions in a chemical compound were obtained by Kistner and Sunyar in 1960. From these beginnings the technique of Mossbauer spectroscopy rapidly emerged and the astonishing versatility of this new technique soon led to its extensive application to a wide variety of chemical and solid-state problems. This book reviews the results obtained by Mossbauer spectroscopy during the past ten years in the belief that this will provide a firm basis for the continued development and application of the technique to new problems in the future. It has been our aim to write a unified and consistent treatment which firstly presents the basic principles underlying the phenomena involved, then outlines the experimental techniques used, and finally summarises the wealth of experimental and theoretical results which have been obtained. We have tried to give some feeling for the physical basis of the Mossbauer effect with­ out extensive use of mathematical formalism, and some appreciation of the experimental methods employed without embarking on a detailed discussion of electronics and instrumentation. However, full references to the original literature are provided and particular points can readily be pursued in more detail if required. Moessbauer Spectroscopy ......Page 1 Contents ......Page 3 Preface ......Page 9 1 The Moessbauer Effect ......Page 11 1.1 Energetics of Free-atom Recoil and Thermal Broadening ......Page 12 1.2 Heisenberg Natural Linewidth ......Page 15 1.3 Energy and Momentum Transfer to the Lattice ......Page 16 1.4 Recoil-free Fraction and Debye-Waller Factor ......Page 19 1.5 Cross-section for Resonant Reabsorption ......Page 21 1.6 A Moessbauer Spectrum ......Page 25 References ......Page 26 2.1 Velocity Modulation of Gamma-rays ......Page 27 2.2 Constant-velocity Drives ......Page 29 2.3 Repetitive Velocity-scan Systems ......Page 31 2.4 Derivative Spectrometers ......Page 36 2.5 Scattering Experiments ......Page 37 2.6 Source and Absorber Preparation ......Page 40 2.7 Detection Equipment ......Page 45 2.8 Cryogenic Equipment and Ovens ......Page 48 2.9 Velocity Calibration ......Page 49 2.10 Curve Fitting by Computer ......Page 51 References ......Page 53 3.1 Chemical Isomer Shift ......Page 56 3.2 Second-order Doppler Shift and Zero-point Motion ......Page 60 3.3 Effect of Pressure on the Chemical Isomer Shift ......Page 63 3.4 Electric Quadrupole Interactions ......Page 64 3.5 Magnetic Hyperfine Interactions ......Page 69 3.6 Combined Magnetic and Quadrupole Interactions ......Page 73 3.7 Relative Intensities of Absorption Lines ......Page 76 3.8 Relaxation Phenomena ......Page 82 3.9 Anisotropy of the Recoilless Fraction ......Page 84 3.10 The Pseudoquadrupole Interaction ......Page 86 References ......Page 88 4.1 Relativity and General Physics ......Page 90 4.2 Nuclear Physics ......Page 92 4.3 Solid-state Physics and Chemistry ......Page 94 References ......Page 96 5.1 The Gamma-decay Scheme ......Page 97 5.2 Source Preparation and Calibration ......Page 99 5.3 Chemical Isomer Shifts ......Page 100 5.4 Quadrupole Splittings ......Page 106 5.5 Magnetic Interactions ......Page 112 5.6 Polarised Radiation Studies ......Page 114 5.7 Energetic Nuclear Reactions ......Page 119 References ......Page 120 6 High-spin Iron Complexes ......Page 122 6.1 Iron(II) Halides ......Page 123 6.2 Iron(II)\rSalts of Oxyacids and Other Anions ......Page 140 6.3 Iron(II)\rComplexes with Nitrogen Ligands ......Page 150 6.4 Iron(III) Halides ......Page 158 6.5 Iron(III) Salts of Oxyacids ......Page 165 6.6 Iron(III) Complexes with Chelating Ligands ......Page 169 References ......Page 174 7.1 Ferrocyanides ......Page 179 7.2 Ferricyanides ......Page 183 7.3 Prussian Blue ......Page 188 7.4 Substituted Cyanides ......Page 192 7.5 Chelating Ligands ......Page 197 References ......Page 201 8.1 Iron(II) Compunds Showing 5T2-1A1 \rCrossover ......Page 204 8.2 Iron(III) Compounds Showing 6A1-2T2 Crossover ......Page 212 8.3 Iron(II) Compounds with S=1 Spin State ......Page 215 8.4 Iron(III) Compounds with S=3/2 Spin State ......Page 216 8.5 Iron 1,2-Dithiolate Complexes ......Page 222 8.6 Systems Containing Iron(I), Iron(IV), and Iron(VI\r) ......Page 226 References ......Page 229 9 Covalent Iron Compounds ......Page 231 9.1 Binary Carbonyls, Carbonyl Anions, and Hydride Anions ......Page 232 9.2 Substituted Iron Carbonyls ......Page 236 9.3 Ferrocene and other Pi-Cyclopentadienyl Derivatives ......Page 243 References ......Page 247 10 Iron Oxides and Sulphides ......Page 249 10.1 Binary Oxides and Hydroxides ......Page 250 10.2 Spinel Oxides AB2O4 ......Page 268 10.3 Other Ternary Oxides ......Page 279 10.4 Iron(IV) Oxides ......Page 290 10.5 Iron Chalcogenides ......Page 293 10.6 Silicate Minerals ......Page 296 10.7 Lunar Samples ......Page 304 References ......Page 306 11 Alloys and Intermetallic Compounds ......Page 314 11.1 Metallic Iron ......Page 315 11.2 Iron Alloys ......Page 318 11.3 Intermetallic Compounds ......Page 327 References ......Page 335 12 57Fe Impurity Studies ......Page 339 12.1 Chemical Compounds ......Page 340 12.2 Metals ......Page 350 12.3 Miscellaneous Topics ......Page 354 References ......Page 358 13 Biological Compounds ......Page 362 13.1 Haemeproteins ......Page 363 13.2 Metalloproteins ......Page 375 References ......Page 379 14.1 Gamma-decay Scheme and Sources ......Page 381 14.2 Hyperfine Interactions ......Page 385 14.3 Tin(II) Compounds ......Page 391 14.4 Inorganic Tin(IV) Compounds ......Page 400 14.5 Organotin(IV) Compounds ......Page 409 14.6 Metals and Alloys ......Page 427 References ......Page 434 15.1 Potassium ......Page 443 15.2 Germanium ......Page 444 15.3 Krypton ......Page 447 15.4 Antimony ......Page 451 15.5 Tellurium ......Page 462 15.6 Iodine ......Page 472 15.7 Xenon ......Page 492 15.8 Caesium ......Page 496 15.9 Barium ......Page 498 References ......Page 499 16.1 Nickel ......Page 503 16.2 Zinc ......Page 507 16.4 Ruthenium ......Page 509 16.6 Hafnium ......Page 514 16.7 Tantalum ......Page 517 16.8 Tungsten ......Page 519 16.10 Osmium ......Page 524 16.11 Iridium ......Page 528 16.12 Platinum ......Page 534 16.13 Gold ......Page 536 16.14 Mercury ......Page 540 References ......Page 542 17 The Rare-earth Elements ......Page 546 17.2 Neodymium ......Page 547 17.4 Samarium ......Page 549 17.5 Europium ......Page 553 17.6 Gadolinium ......Page 568 17.8 Dysprosium ......Page 573 17.9 Holmium ......Page 583 17.10 Erbium ......Page 584 17.11 Thulium ......Page 589 17.12 Ytterbium ......Page 595 References ......Page 600 18.2 Protactinium ......Page 606 18.3 Uranium ......Page 607 18.4 Neptunium ......Page 610 References ......Page 614 Appendix 1. Table of nuclear data for Moessbauer transitions ......Page 617 Appendix 2. The relative intensities of hyperfine lines ......Page 622 Notes on the International System of Units (SI) ......Page 629 Author Index ......Page 631 Subject Index ......Page 655