Vibrational Effects in the Thermal Expansion of Noncubic Solids

Abstract

The thermodynamics of thermal expansion and of the related Grüneisen function γ(T, V) is discussed first for cubic and isotropic solids. Vibrational effects are treated in the quasiharmonic approximation. For central force models two effects are distinguished-that of the anharmonicity of the pair potential, normally contributing positively to the expansion, and that of the bond ``tensions,'' contributing negatively. The extension of the theory to noncubic solids is summarized, the strongly anisotropic example of zinc being used to illustrate the roles played by anisotropy in the elasticity and in the Grüneisen tensor. Recent work on central force lattice models, both ionic and nonionic, is reviewed. For ``internal expansion,'' in which the disposition of atoms within a unit cell varies with temperature, it is convenient to treat both internal and external strains on the same footing.