The Chemical Structure of Solids

of Volume 1.- 1 Chemical Bonds in Solids.- 1. Why Solids Are Different from Molecules.- 1.1. Quantum Theory of Chemical Bonds.- 1.2. The Five Solid Types.- 1.3. Bonds and/or Bands?.- 2. Crystal Structures and Cohesive Energies of the Elements.- 2.1. Valence Groupings.- 2.2. Shell Effects.- 2.3. Transition Series.- 3. Binary Compounds and Alloys.- 3.1. Minerals.- 3.2. Semiconductors.- 3.3. Intermetallic Solutions.- 4. Chemical Bonding and Physical Properties.- 4.1. Classical Polarizabilities.- 4.2. Dispersion.- 4.3. Covalent and Ionic Energies.- 4.4. Chemical Trends in Physical Properties.- 5. Summary.- References.- 2 Energy Bands.- 1. Introduction.- 1.1. Historical Remarks.- 1.2. The Independent-Electron Approximation.- 2. Energy Bands in General.- 3. The Classical Descriptions of Energy Bands in Periodic Systems.- 3.1. Introduction.- 3.2. Two Classical Limits-Tight Binding and Nearly Free Electron.- 3.3. Tight Binding Theory.- 3.4. Wannier Functions.- 3.5. Nearly-Free-Electron Theory.- 3.6. Pseudopotentials.- 3.7. The Cellular Method.- 3.8. Orthogonalized Plane Wave, Augmented Plane Wave, and Related Methods.- 4. Approximations, Interpolations, Perturbations.- 4.1. Introduction.- 4.2. Moment Methods.- 4.3. Nearly-Free-Electron Perturbation Theory.- 4.4. The k * p Method.- 4.5. Small-k Expansions for KKR Theory.- 5. Some Relevant Experiments.- 5.1. Introduction.- 5.2. Soft X-Ray Emission and Absorption.- 5.3. Optical Spectroscopy.- 5.4. Fermi Surface Analysis.- 6. Typical Band Structures.- 6.1. Introduction.- 6.2. Simple Metals.- 6.3. Alkali Halides.- 6.4. Group IV Semiconductors.- 6.5. The III-V and II-VI Semiconductors.- 6.6. Silicon Dioxide.- 6.7. Transition Metals.- 6.8. Transition Metal Compounds.- 7. Disordered Solids.- 7.1. Introduction.- 7.2. Definition of Problems.- 7.3. The Density of States in an Alloy.- 7.4. The Anderson Problem.- 7.5. Topological Disorder.- 7.6. Applications.- 8. Conclusion.- Acknowledgments.- References.- 3 Factors Controlling the Formation and Structure of Phases.- 1. Introduction.- 2. Practical Prediction of Phase Stability.- 2.1. Metals: Use of Thermodynamic Data.- 2.2. Valence Compounds: Use of Crystal Chemical Knowledge.- 3. General Structural Consequences of Bonding Types.- 3.1. Ionic Crystals.- 3.2. Compounds with Saturated Covalent Bonds.- 3.3. Metallic Phases.- 3.4. A Priori Separation of Structure Types.- 4. Atomic Size and Structural Constraint.- 5. Factors Influencing the Stability of Crystal Structures.- 5.1. Electrochemical Factor.- 5.2. Geometric Effects.- 5.3. Energy Band Effects.- 5.4. Environmental Factors.- 6. Distortions of Crystal Structures.- 6.1. Distortions Arising from Cation-Cation Bonds.- 6.2. Jahn-Teller Distortions.- 6.3. Spin-Orbit Coupling Distortions.- 6.4. Magnetic Exchange Energies.- 6.5. Mechanical Instability.- 7. Epilogue.- Appendix-Structure Diagrams.- Acknowledgments.- References.- 4 Structure and Composition in Relation to Properties.- 1. Magnetic Behavior.- 1.1. Introduction.- 1.2. The 3d Transition Elements.- 1.3. Rare Earth Metals.- 1.4. Role of Local Atomic Environment Regarding Development of Atomic Moments and Long-Range Order.- 1.5. Directional Ordering and Magnetic Anisotropy.- 1.6. Magnetic Oxides.- 1.7. Magnetic Semiconductors.- 1.8. Linear and Two-Dimensional Magnetic Behavior.- 1.9. Amorphous Magnetic Materials.- 1.10. Summary.- 2. Superconducting Behavior.- 2.1. Introduction.- 2.2. The Cr3Si (?-W) and Transition Metal Nitride and Carbide Phases. Electron Concentration and Lattice Instability.- 2.3. Role of Stoichiometry and Atomic Order.- 2.4. Metastable Superconducting Phases.- 2.5. Paramagnetic Impurities in Superconductors.- 2.6. Ternary Superconducting Chalcogenides.- 2.7. Superconductivity of Degenerate Semiconductors.- 2.8. Summary.- 3. Dielectric Materials.- 3.1. Ferroelectrics.- 3.2. Piezoelectrics.- 3.3. Nonlinear Optical Materials.- 3.4. Electrooptic and Pyroelectric Materials.- 3.5. Summary.- 4. Mechanical Behavior.- 4.1. Introduction.- 4.2. Elastic Behavior.- 4.3. Plastic Behavior.- 4.4. Summary.- Acknowledgments.- References.- 5 Introduction to Chemical and Structural Defects in Crystalline Solids.- 1. Introduction.- 2. Point Defects.- 3. Dislocations.- 4. Planar Defects.- 5. Volumetric Defects.- Acknowledgments.- References.- 6 Defect Equilibria in Solids.- 1. Introduction.- 1.1. Native Defects.- 1.2. Law of Mass Action and Point Defects.- 1.3. Electronic Defects.- 1.4. Energetics of Defect Formation.- 2. Native Defects.- 2.1. Defect Equilibria in Elemental Crystals.- 2.2. Defect Equilibria in Binary Compounds.- 2.3. Nonstoichiometry-Equilibria with External Phases.- 2.4. Ionization of Defects.- 2.5. Relationship between Mass Action Law and Statistical Thermodynamics.- 2.6. Defect Interactions.- 3. Multicomponent Systems.- 3.1. Equilibria Involving Foreign Atoms.- 3.2. Multicomponent Compounds.- 4. Extended Defects.- Acknowledgment.- References.- 7 Characterization of Solids-Chemical Composition.- 1. Introduction.- 2. Current Capability for Determination of Chemical Composition.- 2.1. Introduction.- 2.2. General Over iew.- 2.3. Analytical Techniques: Present Status.- 2.4. Precision and Sensitivity of Analytical Techniques.- 3. Application of Current Techniques to Characterization of Materials.- 3.1. Characterization of Major Phase.- 3.2. Characterization of Minor Phases and Impurities.- 3.3. Characterization of Surfaces.- 4. Utilization of Existing Techniques.- 4.1. Literature Examples.- 4.2. Factors Determining Use.- Acknowledgments.- References.- 8 Structural Characterization of Solids.- 1. Introduction.- 2. Structural Characterization by Optical Techniques.- 2.1. Morphology.- 2.2. Bulk Optical Properties.- 2.3. Scattering Studies.- 2.4. Surface Characterization.- 2.5. Particle Size and Shape.- 3. Structural Characterization by X-Ray Diffraction.- 3.1. X-Ray Powder Methods.- 3.2. Single-Crystal X-Ray Methods.- 3.3. Temperature and Pressure Experiments.- 3.4. X-Ray Topography and Interferometry.- 4. Electron Methods for Materials Characterization.- 4.1. Electron Microscopy.- 4.2. Electron Diffraction.- 4.3. Scanning Electron Microscopy.- 5. Neutron Scattering from Solids.- 5.1. Neutron Sources.- 5.2. Interactions with Matter.- 5.3. Structure Analysis with Neutrons.- 5.4. Magnetic Structure Analysis.- 5.5. Lattice and Spin Dynamics.- 6. Spectroscopy and Local Symmetry.- 6.1. Absorption Spectra in the Visible Range.- 6.2. Infrared Absorption Spectroscopy.- 6.3. Raman Spectra.- 6.4. Soft X-Ray Spectra.- 6.5. Electron Spin Resonance.- 6.6. Nuclear Magnetic Resonance.- 6.7. Mossbauer Effect.- 6.8. Electron Spectroscopy.- 6.9. Acoustic Spectroscopy.- 7. Physical Properties as Characterization Tools.- 7.1. Introduction.- 7.2. Some Crystal Physical Generalizations.- 7.3. Dielectric Measurements.- 7.4. Electrical Characterization of Solids.- 7.5. Magnetic Measurements.- 7.6. Calorimetric Measurements.- Acknowledgment.- References.