Introduction to Structural Chemistry (eBook)

1. Atom1.1.  Ionization potentials and electron affinities    1.1.1. Ionization potentials of atoms    1.1.2. Electron affinity1.2. Effective nuclear charge1.3. Absolute dimensions of atoms1.4. Radii of atoms in molecules and crystals    1.4.1. Historical outline    1.4.2. Metallic radii    1.4.3. Covalent radii1.5. Radii of ions in molecules and crystals    1.5.1. Methods of estimating ionic radii    1.5.2. Experimental (bonded) ionic radii    1.5.3. Energy-derived ionic radii    1.5.4. Ultimate ionic radii2. Chemical bond2.1. Historical development of the concept2.2. Types of bonds: covalent, ionic, polar, metallic    2.2.1. Ionic bond    2.2.2. Covalent bond    2.2.3. Polar bond, effective charges of atoms    2.2.4. Metallic bond    2.2.5. Effective valences of atoms2.3. Energies of the chemical interactions of atoms    2.3.1. Bond energies in molecules and radicals    2.3.2. Bond energies in crystals    2.3.3. Crystal lattice energies    2.3.4. Band gaps in solids2.4. Concept of electronegativity    2.4.1. Discussion about electronegativity    2.4.2. Thermochemical electronegativities     2.4.3. Ionization electronegativities    2.4.4. Geometrical electronegativities    2.4.5. Recommended system of electronegativities of atoms and     radicals    2.4.6. Equalization of electronegativities and atomic charges2.5. Effective charges of atoms and chemical behavior2.6. Change of chemical bond character under pressure2.7. Conclusions3. “Small” molecule.3.1. Introduction3.2. Inorganic molecules and radicals    3.2.1. Bond distances    3.2.2. Bond angles. VSEPR concept    3.2.3. Non-stoichiometric and unusual molecules 3.3. Organic molecules3.4. Organometallic compounds3.5. Clusters    3.5.1. Boron clusters    3.5.2. Transition metal clusters    3.5.3. Clusters of main group elements    3.5.4. Fullerenes3.6. Coordination compounds4. Intermolecular forces4.1. Van der Waals interaction4.2. Interdependence of the lengths of covalent and van der Waals bonds4.3. Van der Waals radii    4.3.1. Introduction    4.3.2. Crystallographic van der Waals radii    4.3.3. Equilibrium radii of atoms    4.3.4. Anisotropic van der Waals radii    4.3.5. Concluding remarks4.4. Donor-acceptor interactions4.5. Hydrogen bond5. Crystal structure – idealised5.1.  Structures of elements    5.1.1. Structures of metals    5.1.2. Structures of non-metals5.2. Binary inorganic crystalline compounds    5.2.1 Crystal structures of halides, oxides, chalcogenides, pnictides    5.2.2 Structures of compounds with diverse bonds5.3. Interconversions of crystal structures5.4. Effective coordination number 5.5. Bond valence (bond strength, bond order) 5.6. Ternary compounds5.7. Structural features of silicates6. Crystal structure – real6.1. Thermal motion6.2. Lindemann’s hypothesis6.3. Defects in crystals    6.3.1. Classification of defects    6.3.2. Defects induced by shock waves    6.3.3. Real structure and melting of solids6.4. Isomorphism and solid solutions7. Amorphous state7.1. Dispersing powders7.2. Amorphous solids, glasses7.3. Structure of melts7.4. Structure of aqueous solutions  8. Between molecule and solid8.1. Energetic properties of clusters and nanoparticles    8.1.1. Melting temperatures and heats under transition from bulk to nanophases    8.1.2. Energy variation under transition from bulk to clusters8.2. Changes of atomic structure on transition from bulk solids to nanophases8.3. Size effect in the dielectric permittivity of crystals    8.3.1. Effect of the energy factor    8.3.2. Effect of the phase composition on ε of barium titanate    8.3.3. Dielectric behavior of ceramic materials    8.3.4. Dielectric properties of multi-phase systems8.4. Conclusions9. Phase transitions 9.1. Polymorphism    9.1.1. Polyamorphism9.2 Energies of phase transitions    9.2.1. Melting heats of compounds    9.2.2. Sublimation heats of elements and compounds    9.2.3. Evaporation heats of compounds    9.2.4. Enthalpies of phase transformations10. Extreme conditions10.1. Polymorphic transformations under high static pressures10.2. Pressure-induced amorphisation and polyamorphism10.3. Effect of the crystal size on the pressure of phase transition  10.4. Solid phase transformations under high dynamic pressures10.5. Detonation transformation and synthesis of diamond and c-BN 10.6. Equations of state of solids 11. Structure and optical properties11.1. Refractive index    11.1.1. Definitions, anisotropy, theory    11.1.2. Influence of composition, structures and thermodynamic conditions on refractive indices11.2. Polarization and dipole moments11.3. Molecular refraction: experiment and calculation    11.3.1. Formulae of refraction    11.3.2. Dependence of refractions on the structure and thermodynamic parameters    11.3.3. Atomic and covalent refractions    11.3.4. Ionic refractions    11.3.5. Bond refractions11.4. Structural application of refractometry11.5. Structural applications of spectroscopy 11.6. Optical electronegativities