Origins of anisotropic thermal expansion in flexible materials

Abstract

A definition of the Grüneisen parameters for anisotropic materials is derived based on the response of phonon frequencies to uniaxial stress perturbations. This Grüneisen model relates the thermal expansion in a given direction ($α_{ii}$) to one element of the elastic compliance tensor, which corresponds to the Young's modulus in that direction ($Y_{ii}$). The model is tested through ab initio prediction of thermal expansion in zinc, graphite, and calcite using density functional perturbation theory, indicating that it could lead to increased accuracy for structurally complex systems. The direct dependence of $α_{ii}$ on $Y_{ii}$ suggests that materials which are flexible along their principal axes but rigid in other directions will generally display both positive and negative thermal expansion.