Screened hybrid density functionals for solid-state chemistry and physics

Abstract

Density functional theory incorporating hybrid exchange–correlation functionals has been extraordinarily successful in providing accurate, computationally tractable treatments of molecular properties. However, conventional hybrid functionals can be problematic for solids. Their nonlocal, Hartree–Fock-like exchange term decays slowly and incorporates unphysical features in metals and narrow-bandgap semiconductors. This article provides an overview of our group’s work on designing hybrid functionals for solids. We focus on the Heyd–Scuseria–Ernzerhof screened hybrid functional [J. Chem. Phys. 2003, 118, 8207], its applications to the chemistry and physics of solids and surfaces, and our efforts to build upon its successes.

Communication: Singularity-free hybrid functional with a Gaussian-attenuating exact exchange in a plane-wave basis

“…PBE0 shows lower errors than HSE06. 12,13 However, for the case of insulators, we noticed that Gau-PBE shows lower root mean square (rms) errors than PBE0. Notably, at variance with HSE06 and Gau-PBE, the insulator bandgaps calculated using PBE0 fluctuate corresponding to the change of k and q grid meshes, as in the semiconductor bandgaps.…”

“…In particular, Heyd-Scuseria-Ernzerhof (HSE) [8][9][10][11][12] functional, characterized by the usage of a modified Coulomb potential for exact a) Author to whom correspondence should be addressed. Electronic mail:…”

Realization of a p–n junction in a single layer boron-phosphide

“…Since the band gaps are underestimated at the DFT-GGA level, we also carried out calculations using the HSE06 hybrid functional. [35][36][37] A K-point sampling of 11 Â 11 Â 1 was used for the 5 Â 5 supercell. All structures were relaxed using the special Davidson algorithm 38 with simultaneous minimization of the total energy and the interatomic forces.…”

First Principles Calculations on Oxide-Based Heterogeneous Catalysts and Photocatalysts: Problems and Advances

“…Of course, there are also drawbacks. One is the already mentioned high computational cost when plane wave codes are used in combination with hybrid functionals; the other is that hybrid functionals do not work so well for metallic systems, although also in this case there are differences (for instance, the HSE functional seems to perform better for metals than other hybrid functionals [25,96]). This problem is particularly relevant when one is interested in metal/ oxide interfaces (supported oxide films on metals, metal nanoparticles deposited on an oxide support, etc.).…”