Perturbation approach to ab initio effective mass calculations

TL;DR

This paper introduces a perturbation-based method for calculating effective masses within all-electron DFT, demonstrating its accuracy on various semiconductors and applying it to materials with defects.

Contribution

It implements a degenerate perturbation $k ext{·}p$ approach in WIEN2k and discusses its application and limitations for non-local potentials.

Findings

Accurate effective mass calculations for major semiconductors.

Application to graphene and CuI with defects.

Discussion of basis set requirements and potential issues with non-local potentials.

Abstract

A degenerate perturbation $k\cdot p$ approach for effective mass calculations is implemented in the all-electron density functional theory (DFT) package WIEN2k. The accuracy is tested on major group IVA, IIIA-VA, and IIB-VIA semiconductor materials. Then, the effective mass in graphene and CuI with defects is presented as illustrative applications. For states with significant Cu-d character additional local orbitals with higher principal quantum numbers (more radial nodes) have to be added to the basis set in order to converge the results of the perturbation theory. Caveats related to a difference between velocity and momentum matrix elements are discussed in the context of application of the method to non-local potentials, such as Hartree-Fock/DFT hybrid functionals and DFT+U.