Hybrid functionals within the all-electron FLAPW method: implementation and applications of PBE0

TL;DR

This paper introduces an efficient implementation of the PBE0 hybrid functional within the all-electron FLAPW method, enabling accurate electronic structure calculations for semiconductors and insulators, including magnetic materials.

Contribution

The authors develop a computationally efficient approach to incorporate PBE0 hybrid functionals into the FLAPW method, utilizing auxiliary basis functions and symmetry considerations.

Findings

Improved band gap predictions for various semiconductors and insulators.

Correctly predicts EuO as a semiconductor, unlike local functionals.

Achieves favorable convergence in self-consistent calculations.

Abstract

We present an efficient implementation of the PBE0 hybrid functional within the full-potential linearized augmented-plane-wave (FLAPW) method. The Hartree-Fock exchange term, which is a central ingredient of hybrid functionals, gives rise to a computationally expensive nonlocal potential in the one-particle Schroedinger equation. The matrix elements of this exchange potential are calculated with the help of an auxiliary basis that is constructed from products of FLAPW basis functions. By representing the Coulomb interaction in this basis the nonlocal exchange term becomes a Brillouin-zone (BZ) sum over vector-matrix-vector products. We show that the Coulomb matrix can be made sparse by a suitable unitary transformation of the auxiliary basis, which accelerates the computation of the vector-matrix-vector products considerably. Additionally, we exploit spatial and time-reversal symmetry to identify the nonvanishing exchange matrix elements in advance and to restrict the k summations for the nonlocal potential to an irreducible set of k points. Favorable convergence of the self-consistent-field cycle is achieved by a nested density-only and density-matrix iteration scheme. We discuss the convergence with respect to the parameters of our numerical scheme and show results for a variety of semiconductors and insulators, including oxide materials, where the PBE0 hybrid functional improves the band gaps and the description of localized states in comparison with the PBE functional. Furthermore, we find that in contrast to conventional local exchange-correlation functionals ferromagnetic EuO is correctly predicted to be a semiconductor.