Finite temperature external potential in crystalline solids

TL;DR

This paper generalizes the correction of external potentials in crystalline solids at finite temperature, enabling ab initio calculations of thermal-averaged properties without dynamical information.

Contribution

It extends Allen's pseudopotential correction to the full crystal potential at finite temperature, transforming Kasowski's empirical study into an ab initio framework.

Findings

Provides a formalism for finite temperature crystal potentials

Enables ab initio finite temperature band structure calculations

Uses experimental Debye-Waller factors for validation

Abstract

Thermal vibrations alter the external potential. Allen (Phys. Rev. B 18 (1978) 5217) proved that at finite temperatures the pseudopotential form factors are corrected by a Debye-Waller Factor (DWF). We generalize this result to the crystal potential. (The generalization to the all-electron case of the nuclear potential fails due to the breakdown of the rigid-atom approximation.) This finite temperature formalism only gives thermal-averaged properties and no dynamical information can be obtained. Hence, it is labeled the Quasi Ab Initio formalism. Analogous to the use of experimental lattice parameters in ab initio studies, experimental DWF can also be used. The justification is identical; the experimental parameters can be validated by separate ab initio studies. Our work transforms, forty years later, Kasowski's empirical study (Phys. Rev. B. 8 (1973) 1378) into the first ab initio finite temperature band structure calculation. This formalism opens the way to obtain ab initio finite temperature thermal-averaged properties from a single calculation.