Length-gauge optical matrix elements in WIEN2k

TL;DR

This paper demonstrates the implementation of length-gauge optical matrix elements in the WIEN2k all-electron package, enabling more accurate optical property calculations for materials with non-local exchange-correlation potentials.

Contribution

The authors developed a finite difference approach to compute length-gauge matrix elements in WIEN2k, previously inaccessible, and illustrated it with several semiconductor and 2D material examples.

Findings

Length-gauge matrix elements can be computed in WIEN2k using the proposed method.

Non-local exchange potentials significantly enhance oscillator strengths.

An analytical expression for the enhancement factor was derived.

Abstract

Hybrid exchange-correlation functionals provide superior electronic structure and optical properties of semiconductors or insulators as compared to semilocal exchange-correlation potentials due to admixing a portion of the non-local exact exchange potential from a Hartree-Fock theory. Since the non-local potential does not commute with the position operator, the momentum matrix elements do not fully capture the oscillator strength, while the length-gauge velocity matrix elements do. So far, length-gauge velocity matrix elements were not accessible in the all-electron full-potential WIEN2k package. We demonstrate the feasibility of computing length-gauge matrix elements in WIEN2k for a hybrid exchange-correlation functional based on a finite difference approach. To illustrate the implementation we determined matrix elements for optical transitions between the conduction and valence bands in GaAs, GaN, (CH$_3$NH$_3$)PbI$_3$ and a monolayer MoS$_2$. The non-locality of the Hartree-Fock exact exchange potential leads to a strong enhancement of the oscillator strength as noticed recently in calculations employing pseudopotentials [Laurien and Rubel: arXiv:2111.14772 (2021)]. We obtained an analytical expression for the enhancement factor in terms of the difference in eigenvalues not captured by the kinetic energy. It is expected that these results can also be extended to other non-local potentials, e.g., a many-body $GW$ approximation.