On the accuracy of the HSE hybrid functional to describe many-electron interactions and charge localization in semiconductors

Abstract

Hybrid functionals, which mix a fraction of Hartree-Fock (HF) exchange with local or semilocal exchange, have become increasingly popular in quantum chemistry and computational materials science. Here, we assess the accuracy of the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional to describe many-electron interactions and charge localization in semiconductors. We perform diffusion quantum Monte Carlo (DMC) calculations to obtain the accurate ground-state spin densities of the negatively charged (SiV)${}^{-}$ and the neutral (SiV)${}^0$ silicon-vacancy center in diamond, and of the cubic silicon carbide (3C-SiC) with an extra electron. We compare our DMC results with those obtained with the HSE functional and find a good agreement between both methods for (SiV)${}^{-}$ and (SiV)${}^0$, whereas the correct description of 3C-SiC with an extra electron crucially depends on the amount of HF exchange included in the functional. Also, we examine the case of the neutral Cd vacancy in CdTe, for which we assess the performance of HSE against the many-body \emph{GW} approximation for the description of the position of the defect states in the band gap.

References in corpus (48)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Quantum Cryptography
• Advanced capabilities for materials modelling with Quantum ESPRESSO
• Climbing the Density Functional Ladder: Non-Empirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids
• Optimized norm-conserving Vanderbilt pseudopotentials
• The PseudoDojo: Training and grading a 85 element optimized norm-conserving pseudopotential table
• Pseudopotentials for high-throughput DFT calculations
• Van der Waals Energies in Density Functional Theory
• Self-consistent hybrid functional for condensed systems
• The electronic structure of the silicon vacancy color center in diamond
• Continuum variational and diffusion quantum Monte Carlo calculations
• A stable compound of helium and sodium at high pressure
• Jastrow correlation factor for atoms, molecules, and solids
• Fractional spins and static correlation error in density functional theory
• Density functional with full exact exchange, balanced nonlocality of correlation, and constraint satisfaction
• Beyond the locality approximation in the standard diffusion Monte Carlo method
• Finite-size errors in continuum quantum Monte Carlo calculations
• Electronic structure of the negatively-charged silicon-vacancy center in diamond
• Double-hybrid density-functional theory made rigorous
• {\emph{Ab initio} magneto-optical spectrum of Group-IV -- Vacancy color centers in diamond
• Optical signatures of silicon-vacancy spins in diamond
• Predictive GW calculations using plane waves and pseudopotentials
• An \emph{ab initio} study on split silicon-vacancy defect in diamond: electronic structure and related properties
• Smooth relativistic Hartree-Fock pseudopotentials for H to Ba and Lu to Hg
• Dual behavior of excess electrons in rutile TiO2
• Norm-conserving Hartree-Fock pseudopotentials and their asymptotic behavior
• Ultrafast, all-optical coherent control of single silicon vacancy colour centres in diamond
• Hybrid-functional calculations with plane-wave basis sets: The effect of the singularity correction on total energies, energy eigenvalues, and defect energy levels
• \emph{Ab initio} calculation of spin-orbit coupling for NV center in diamond exhibiting dynamic Jahn-Teller effect
• Theory of the optical spinpolarization loop of the nitrogen-vacancy center in diamond
• Photoluminescence excitation spectroscopy of SiV${}^{-}$ and GeV${}^{-}$ color center in diamond
• The neutral silicon-vacancy center in diamond: spin polarization and lifetimes
• Mind the gap but also the spin: why the Heyd-Scuseria-Ernzerhof hybrid functional description of VO2 phases is not correct
• The Schottky defect formation energy in MgO calculated by diffusion Monte Carlo
• Coherence properties and quantum control of silicon vacancy color centers in diamond
• Wave functions for quantum Monte Carlo calculations in solids: Orbitals from density functional theory with hybrid exchange-correlation functionals
• Theoretical unification of hybrid-DFT and DFT+U methods for the treatment of localized orbitals
• Structural Stability and Defect Energetics of ZnO from Diffusion Quantum Monte Carlo
• On-Demand Generation of Neutral and Negatively-Charged Silicon-Vacancy Centers in Diamond
• Diffusion quantum Monte Carlo study of the equation of state and point defects in aluminum
• Vibrational modes of negatively charged silicon-vacancy centers in diamond from ab initio calculations
• Diffusion quantum Monte Carlo calculations of SrFeO${}_3$ and LaFeO${}_3$
• Static correlation beyond the random phase approximation: Dissociating H2 with the Bethe-Salpeter equation and time-dependent GW
• Self-compensation in phosphorus-doped CdTe
• First-principles DFT + GW study of the Te antisite in CdTe
• Defect properties of Sn- and Ge-doped ZnTe: Suitability for intermediate-band solar cells
• Hybrid-DFT+V${}_w$ method for accurate band structure of correlated transition metal compounds: the case of cerium dioxide
• Origin of the anomalous semiconducting behaviour in dense lithium

Cited by in corpus (2)

• Can we rely on hybrid-DFT energies of solid-state problems with local-DFT geometries?
• Defect engineering of ultrathin gallium nitride via electric fields for advanced electronic, magnetic, and gas sensing applications