Nonunique fraction of Fock exchange for defects in two-dimensional materials

Abstract

By investigating the vacancy and substitutional defects in monolayer WS${}_2$ with hybrid functionals, we find that there is no unique amount of Fock exchange that concurrently satisfies the generalized Koopmans' condition and reproduces the band gap and band-edge positions. Fixing the mixing parameter of Fock exchange based upon the band gap can lead to qualitatively incorrect defect physics in two-dimensional materials. Instead, excellent agreement is achieved with experiment and many-body perturbation theory within $GW$ approximation once the mixing parameters are tuned individually for the defects and the band edges. We show the departure from a unique optimized mixing parameter is inherent to two-dimensional systems as the band edges experience a reduced screening whilst the localized defects are subject to bulklike screening.

Main manuscript (7 pages, 3 figures) with supplemental material (3 pages, 5 figures)