Low-Frequency Vibrations of Inorganic and Coordination Compounds

1 Introduction.- 1.1. History.- 1.2. Usefulness of the Far-Infrared Region.- 1.3. Problems and Remedies.- Instrumental Problems.- Source.- Detector.- Amplification.- Miscellaneous Problems.- Sampling Problems.- Interpretative Problems.- 2 Far-Infrared Instrumentation.- 2.1. Introduction.- 2.2. Present Commercial Grating/Prism Instruments.- Beckman Prism and/or Grating Instruments.- IR-11 Infrared Spectrophotometer.- IR-12, IR-9, and IR-20 Infrared Spectrophotometers.- Perkin-Elmer Prism and/or Grating Instruments.- Model 301.- Model 621.- Model 225.- Hitachi FIS-3.- Grubb Parsons Prism and/or Grating Instruments.- Grubb Parsons DM 4.- Grubb Parsons GM 3.- 2.3. Present Commercial Interferometric Instruments.- Types of Interferometers.- Michelson Interferometers.- FS-720 and FS-820.- Grubb Parsons/N.P.L. Cube Interferometer MK 11.- Grubb Parsons Iris Interferometric Spectrometer.- Dunn Associates, Inc., Block FTS-16.- Dunn Associates, Inc., Block FTS-14.- Coderg Co. MIR 2.- Lamellar Grating Interferometers.- Beckman Instruments Co. LR-100.- Perkin-Elmer Corp. Model 180.- 2.4. Comparison of the Interferometer with the Conventional Spectrometer.- 2.5. Trends in Far-Infrared Instrumentation.- 3 Sampling Techniques and Instrument Calibration in the Far-Infrared Region.- 3.1. Introduction.- 3.2. Window Materials for Cells.- Plastic Windows.- Salt-Type Windows.- Silicon, Germanium, and Diamond Windows.- Quartz and Mica.- 3.3. Far-Infrared Solvents.- 3.4. Sampling Techniques.- 3.5. Calibration of Far-Infrared Instruments.- Rotation Spectra of Gases.- Mercury Lines.- Mercuric Oxide.- 4 New Techniques Used with Far-Infrared Measurements.- 4.1. Introduction.- 4.2. The Slow-Neutron Scattering (SNS) Technique.- Theory.- Instrumentation.- Applications.- 4.3. High-Pressure Techniques in the Far-Infrared Region.- Instrumentation.- Applications.- Lattice Vibrations.- Internal Vibrations.- 5 Metal-Oxygen Vibrations.- 5.1. Metal-Oxygen Vibrations in Hydrates.- 5.2. Metallic Oxides.- 5.3. Metal-Oxygen Vibrations in Hydroxyl-Bridged Complexes.- 5.4. Metal-Oxygen Vibrations in Salts Involving Oxygenated Polyatomic Anions.- D3h Symmetry—Nitrates, Carbonates, and Borates.- Td Symmetry—Sulfates, Selenates, Phosphates, Tungstates, Permanganates, Chromates, Molybdates, and Perchlorates.- C3? Symmetry—Chlorates, Bromates, Iodates, Sulfites, and Selenites.- 5.5. ?-Diketone Complexes.- 5.6. Complexes of Organic Acids.- Oxalato Complexes.- Amino Acid Complexes.- Glycolato Complexes.- Biuret Complexes.- 5.7. Complexes of Organic Oxide Ligands.- 5.8. Miscellaneous Complexes.- Peroxy Complexes.- Alkoxides.- Aluminates.- Sulfoxide Complexes.- 5.9. Nature of the Metal-Oxygen Vibration.- 5.10. Raman Spectroscopic Studies.- 6 Metal-Halide Vibration.- 6.1. Introduction.- 6.2. Hepta- and Octacoordinated Molecules—MX7, MX8 (CN = 7, 8).- 6.3. Hexacoordinated Molecules—Oh Symmetry (CN = 6).- The Hexafluorides—MX6 (Gaseous).- Anionic Hexahalides (MX6n-).- Hexafluorides (MF6n-).- Other Hexahalides (MX6n-, X = Cl, Br, I).- 6.4. Pentacoordinated Molecules—MX5, MX5n- (CN = 5).- 6.5. Tetracoordinated Molecules—MX4, MX4n- (CN = 4).- Tetrahedral Molecules and Ions.- Square Planar Ions—MX4n-.- 6.6. Tricoordinated Molecules—MX3 (CN = 3).- 6.7. Dicoordinated Molecules—MX2 (CN = 2).- Gaseous MX2 Compounds.- Solid MX2 Compounds.- 6.8. MX-Type Metal Halides.- 6.9. Miscellaneous Metal Halide Vibrations.- Oxyhalides.- Xenon Halides.- 6.10. Complexes Involving Organic Ligands.- LXM- and LMX2-Type Complexes.- LMX3- and LMX3--Type Complexes.- L2MX2-Type Complexes.- L2M2X4-, L3MX3-, and L4MX2-Type Complexes.- L5MX- and L5MXn--Type Complexes.- LMX5n-, L2MX4n-, and L3MX3n-- Anion-Type Complexes.- 2,2?-Bipyridyl and 1,10-Phenanthroline Complexes.- L3SnX-, L2SnX2-, and LSnCl3-Type Complexes.- Metal Ammine Complexes.- Miscellaneous.- 6.11. Bridged Metal Halide Vibrations.- 6.12. Summary.- Streochemistry and Coordination Number.- Oxidation Number.- Effect of Ligand Field Stabilization Energy on ?mx in Transition Metal Complexes.- Effect of Counter-Ion on ?mx Vibration.- Effect of Mass on ?mx Vibration.- Differentiation Between Bridged and Nonbridged ?mx Vibrations.- 7 Metal-Nitrogen Vibration.- 7.1. Introduction.- 7.2. Metal Ammine Complexes.- 7.3. Complexes of 2,2?-Bipyridyl, 2,2?,2?-Terpyridyl, 1,10-Phenanthroline, Aniline, and 8-Aminoquinoline.- 7.4. Metal-Imidazole Complexes and Complexes with Substituted Imidazoles.- 7.5. Metal-Pyridine and Related Complexes.- LXM2 Complexes.- LMX3 and LMX3- Complexes.- L15MX3 Complexes.- L2(OR)CuX2 Complexes.- L2MX2 Complexes.- Distorted Polymeric Octahedral Complexes.- Polymeric Octahedral Complexes.- Tetrahedral Complexes.- Planar Complexes.- L2MX4, [L2MX4]Y, and L2M3X6 Complexes.- L2MX3 and L3MX2 Complexes.- L4MX2 Complexes.- 7.6. Metal-Ethylenediamine and Related Complexes.- 7.7. Metal-Hydrazine Complexes.- 7.8. Metal Complexes Containing Nitrile Groups.- 7.9. Metal Isothiocyanate and Related Complexes.- 7.10. Metal-Amino Acid Complexes.- 7.11. Metal-Nitro Complexes.- 7.12. Metal-Azide Complexes.- 7.13. Metal-Nitrosyl Complexes.- 7.14. Summary.- Oxidation Number.- Stereochemistry and Coordination Number.- Basicity of Ligand.- 8 Miscellaneous Metal-Ligand Vibrations.- 8.1. Introduction.- 8.2. Metal-Sulfur Vibrations.- 8.3. Metal-Selenium Vibrations.- 8.4. Metal-Tellurium Vibrations.- 8.5. Metal-Phosphorus Vibrations.- 8.6. Metal-Arsenic Vibrations.- 8.7. Metal-Metal Vibrations.- 8.8. Summary of the ?MC and ?MCX Vibrations.- 9 Other Low-Frequency Vibrations.- 9.1. Ion-Pair Vibrations.- 9.2. Low-Frequency Vibrations of Molecules Trapped in Clathrates.- 9.3. Electronic Transitions.- 9.4. Lattice Vibrations.- 9.5. Miscellaneous Vibrations.- Appendixes.- Appendix 1. Selection Rules and Correlation Charts.- Site Symmetries for the 230 Space Groups.- Correlation Tables for the Species of a Group and Its Subgroups.- Appendix 2. Procedure Used for Factor Group Analysis of Solids.