Ionicity of the Chemical Bond in Crystals

The nature of the chemical bond in crystals is discussed. The general theories of L. Pauling based on thermochemical data and of C. A. Coulson based on valence bond concepts are compared with a recent spectroscopic theory. Particular emphasis is placed on binary crystals of formula A^NB^8-N which includes most tetrahedrally coordinated semiconductors as well as crystals of the rocksalt (NaCl) family. A wide range of physical properties is discussed, including crystal structure, energy bands, elastic constants, ionization energies, and impurity states. The role of quantum-mechanical sum rules and spectral moments in constructing simplified models of bond and band behavior is explored. Stress is laid throughout on methods for incorporating quantum-mechanical effects into properties of chemical bonds through algebraic relations rather than through variational solutions of the wave equation.