Fully relativistic $GW$/Bethe-Salpeter calculations in BerkeleyGW: implementation, symmetries, benchmarking, and performance

TL;DR

This paper introduces a fully relativistic implementation of $GW$/Bethe-Salpeter calculations in BerkeleyGW, enabling accurate treatment of materials with strong spin-orbit coupling, and demonstrates its effectiveness through benchmarking on various materials.

Contribution

The authors developed and validated a fully relativistic $GW$/BSE approach with spinor wavefunctions in BerkeleyGW, advancing the accurate modeling of spin-orbit effects in excited-state calculations.

Findings

Quasiparticle band gaps agree with experiments within tens of meV.

The method captures large spin-orbit splittings in optical spectra.

Significant changes in bandstructure for Bi$_2$Se$_3$ compared to DFT.

Abstract

Computing the $GW$ quasiparticle bandstructure and Bethe-Salpeter Equation (BSE) absorption spectra for materials with spin-orbit coupling has commonly been done by treating $GW$ corrections and spin-orbit coupling as separate perturbations to density-functional theory. However, accurate treatment of materials with strong spin-orbit coupling often requires a fully relativistic approach using spinor wavefunctions in the Kohn-Sham equation and $GW$/BSE. Such calculations have only recently become available, in particular for the BSE. We have implemented this approach in the plane-wave pseudopotential $GW$/BSE code BerkeleyGW, which is highly parallelized and widely used in the electronic-structure community. We present reference results for quasiparticle bandstructures and optical absorption spectra of solids with different strengths of spin-orbit coupling, including Si, Ge, GaAs, GaSb, CdSe, Au, and Bi$_2$Se$_3$. The calculated quasiparticle band gaps of these systems are found to agree with experiment to within a few tens of meV. The absorption spectrum of GaSb calculated with the fully-relativistic $GW$-BSE captures the large spin-orbit splitting of peaks in the spectrum. For Bi$_2$Se$_3$, we find a drastic change in the low-energy bandstructure compared to that of DFT, with the fully-relativistic treatment of the $GW$ approximation correctly capturing the parabolic nature of the valence and conduction bands after including off-diagonal self-energy matrix elements. We present the detailed methodology, approach to spatial symmetries for spinors, comparison against other codes, and performance compared to spinless $GW$/BSE calculations and perturbative approaches to SOC. This work aims to spur further development of spinor $GW$/BSE methodology in excited-state research software.