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Journal Articles Physical Review Materials Year : 2023

Hybrid functionals for periodic systems in the density functional tight-binding method

Abstract

Screened range-separated hybrid (SRSH) functionals within generalized Kohn-Sham density functional theory (GKS-DFT) have been shown to restore a general 1/(r epsilon) asymptotic decay of the electrostatic interaction in dielectric environments. Major achievements of SRSH include an improved description of optical properties of solids and correct prediction of polarization-induced fundamental gap renormalization in molecular crystals. The density functional tight-binding method (DFTB) is an approximate DFT that bridges the gap between first-principles methods and empirical electronic structure schemes. While purely long-range corrected RSH are already accessible within DFTB for molecular systems, this work generalizes the theoretical foundation to also include screened range-separated hybrids, with conventional pure hybrid functionals as a special case. The presented formulation and implementation is also valid for periodic boundary conditions (PBC) beyond the Gamma point. To treat periodic Fock exchange and its integrable singularity in reciprocal space, we resort to techniques successfully employed by DFT, in particular a truncated Coulomb operator and the minimum image convention. Starting from the first-principles Hartree-Fock operator, we derive suitable expressions for the DFTB method, using standard integral approximations and their efficient implementation in the DFTB+ software package. Convergence behavior is investigated and demonstrated for the polyacene series as well as two- and three-dimensional materials. Benzene and pentacene molecular and crystalline systems show the correct polarization-induced gap renormalization by SRSH-DFTB at heavily reduced computational cost compared to first-principles methods.

Dates and versions

hal-04173094 , version 1 (28-07-2023)

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Cite

Tammo van der Heide, Bálint Aradi, Ben Hourahine, Thomas Frauenheim, Thomas Niehaus. Hybrid functionals for periodic systems in the density functional tight-binding method. Physical Review Materials, 2023, 7 (6), pp.063802. ⟨10.1103/PhysRevMaterials.7.063802⟩. ⟨hal-04173094⟩

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