Main description:

A concise description of models and quantitative parameters in structural chemistry and their interrelations, with 280 tables and >3000 references giving the most up-to-date experimental data on energy characteristics of atoms, molecules and crystals (ionisation potentials, electron affinities, bond energies, heats of phase transitions, band and lattice energies), optical properties (refractive index, polarisability), spectroscopic characteristics and geometrical parameters (bond distances and angles, coordination numbers) of substances in gaseous, liquid and solid states, in glasses and melts, for various thermodynamic conditions. Systems of metallic, covalent, ionic and van der Waals radii, effective atomic charges and other empirical and semi-empirical models are critically revised. Special attention is given to new and growing areas: structural studies of solids under high pressures and van der Waals molecules in gases. The book is addressed to researchers, academics, postgraduates and advanced-course students in crystallography, materials science, physical chemistry of solids.

Feature:

Ample tables for practical work - not just for illustration

All numbers revised and corrected on most recent data

Covers fast-growing areas: high pressure, nano-matter

Back cover:

Structural chemistry often suffers from fragmented approach, progressing either from the aggregate state (crystallography vs isolated molecule structure), from the method of investigation (X-ray diffraction, spectroscopy, compressibility, etc.) or from the type of substances (inorganic, organometallic, organic). The present book attempts to bridge these gaps, linking the properties of atoms, radicals, molecules, clusters, nano-particles, liquids, solutions, melts, glasses and crystalline solids. Geometrical structure is considered in its indissoluble unity with energetic properties and polarisability (and hence optical properties), using electronegativity as a unifying concept.

Recent decades brought abundant and more precise structural measurements, as well as opening of whole new areas, e.g. non-classical crystals, high-pressure crystallography, real-time study of phase transitions, nanomaterials with their intricate size-effects, fullerenes and clusters, van der Waals molecules. The book gives an outline of these new developments, while showing that the old concepts and techniques, from atomic radii to refractometry, are still useful.

Features:

• A survey of structural chemistry across different aggregate states (gas, liquid, glass, crystalline, nano-materials)
• Conceptual and numerical links between geometrical, thermodynamic, electronic and optical properties
• Up-to-date reference data, systematically presented and tabulated
• Critically revised tables of standard parameters - bond distances and energies, atomic radii, equations of state, etc.

Contents:

1. Atom
1.1.  Ionization potentials and electron affinities
    1.1.1. Ionization potentials of atoms
    1.1.2. Electron affinity
1.2. Effective nuclear charge
1.3. Absolute dimensions of atoms
1.4. Radii of atoms in molecules and crystals
    1.4.1. Historical outline
    1.4.2. Metallic radii
    1.4.3. Covalent radii
1.5. 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 radii

2. Chemical bond
2.1. Historical development of the concept
2.2. 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 atoms
2.3. 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 solids
2.4. 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 charges
2.5. Effective charges of atoms and chemical behavior
2.6. Change of chemical bond character under pressure
2.7. Conclusions

3. “Small” molecule.
3.1. Introduction
3.2. 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 molecules
3.4. Organometallic compounds
3.5. Clusters
    3.5.1. Boron clusters
    3.5.2. Transition metal clusters
    3.5.3. Clusters of main group elements
    3.5.4. Fullerenes
3.6. Coordination compounds

4. Intermolecular forces
4.1. Van der Waals interaction
4.2. Interdependence of the lengths of covalent and van der Waals bonds
4.3. 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 remarks
4.4. Donor-acceptor interactions
4.5. Hydrogen bond

5. Crystal structure – idealised
5.1.  Structures of elements
    5.1.1. Structures of metals
    5.1.2. Structures of non-metals
5.2. Binary inorganic crystalline compounds
    5.2.1 Crystal structures of halides, oxides, chalcogenides, pnictides
    5.2.2 Structures of compounds with diverse bonds
5.3. Interconversions of crystal structures
5.4. Effective coordination number
5.5. Bond valence (bond strength, bond order)
5.6. Ternary compounds
5.7. Structural features of silicates

6. Crystal structure – real
6.1. Thermal motion
6.2. Lindemann’s hypothesis
6.3. 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 solids
6.4. Isomorphism and solid solutions

7. Amorphous state
7.1. Dispersing powders
7.2. Amorphous solids, glasses
7.3. Structure of melts
7.4. Structure of aqueous solutions 

8. Between molecule and solid
8.1. 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 clusters
8.2. Changes of atomic structure on transition from bulk solids to nanophases
8.3. 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 systems
8.4. Conclusions

9. Phase transitions
9.1. Polymorphism
    9.1.1. Polyamorphism
9.2 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 transformations

10. Extreme conditions
10.1. Polymorphic transformations under high static pressures
10.2. Pressure-induced amorphisation and polyamorphism
10.3. Effect of the crystal size on the pressure of phase transition 
10.4. Solid phase transformations under high dynamic pressures
10.5. Detonation transformation and synthesis of diamond and c-BN 10.6. Equations of state of solids

11. Structure and optical properties
11.1. Refractive index
    11.1.1. Definitions, anisotropy, theory
    11.1.2. Influence of composition, structures and thermodynamic conditions on refractive indices
11.2. Polarization and dipole moments
11.3. 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 refractions
11.4. Structural application of refractometry
11.5. Structural applications of spectroscopy 11.6. Optical electronegativities