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

• Published in: arXiv.org
• Main Authors: Chen, Wei, Griffin, Sinéad M, Gian-Marco Rignanese, Hautier, Geoffroy
• Format: Paper
• Language: English
• Published: Ithaca Cornell University Library, arXiv.org 09.10.2022
• Subjects: Defects; Energy gap; Exchanging; Parameters; Perturbation theory; Screening; Two dimensional materials
• ISSN: 2331-8422

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.