Theory of the special displacement method for electronic structure calculations at finite temperature

TL;DR

This paper introduces an advanced special displacement method for accurate, non-perturbative finite-temperature electronic structure calculations, enabling efficient and robust predictions of temperature-dependent properties in solids.

Contribution

The authors extend their previous theory to a reciprocal space formulation, demonstrating that a single supercell calculation with special atomic displacements accurately captures finite-temperature effects.

Findings

Accurate temperature-dependent band structures for 2D and 3D materials.

Reproduction of thermal ellipsoids consistent with X-ray crystallography.

Representation of the special displacement as an exact single-point approximation of Feynman's path integral.

Abstract

Calculations of electronic and optical properties of solids at finite temperature including electron-phonon interactions and quantum zero-point renormalization have enjoyed considerable progress during the past few years. Among the emerging methodologies in this area, we recently proposed a new approach to compute optical spectra at finite temperature including phonon-assisted quantum processes via a single supercell calculation [Zacharias and Giustino, Phys. Rev. B 94, 075125 (2016)]. In the present work we considerably expand the scope of our previous theory starting from a compact reciprocal space formulation, and we demonstrate that this improved approach provides accurate temperature-dependent band structures in three-dimensional and two-dimensional materials, using a special set of atomic displacements in a single supercell calculation. We also demonstrate that our special displacement reproduces the thermal ellipsoids obtained from X-ray crystallography, and yields accurate thermal averages of the mean-square atomic displacements. At a more fundamental level, we show that the special displacement represents an exact single-point approximant of an imaginary-time Feynman's path integral for the lattice dynamics. This enhanced version of the special displacement method enables non-perturbative, robust, and straightforward ab initio calculations of the electronic and optical properties of solids at finite temperature, and can easily be used as a post-processing step to any electronic structure code. Given its simplicity and numerical stability, the present development is suited for high-throughput calculations of band structures, quasiparticle corrections, optical spectra, and transport coefficients at finite temperature.