The Staggered Mesh Method: Accurate Exact Exchange Toward the Thermodynamic Limit for Solids

In periodic systems, the Hartree–Fock (HF) exchange energy exhibits the slowest convergence of all HF energy components as the system size approaches the thermodynamic limit. We demonstrate that the recently proposed staggered mesh method for Fock exchange energy [Xing, Li, and Lin, Math. Comp., 202...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2024-08, Vol.20 (18), p.7958-7968
Main Authors: Quiton, Stephen Jon, Wu, Hamlin, Xing, Xin, Lin, Lin, Head-Gordon, Martin
Format: Article
Language:English
Subjects:
Convergence
Exchanging
Insulators
Quantum Electronic Structure
Thermodynamics
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Summary:In periodic systems, the Hartree–Fock (HF) exchange energy exhibits the slowest convergence of all HF energy components as the system size approaches the thermodynamic limit. We demonstrate that the recently proposed staggered mesh method for Fock exchange energy [Xing, Li, and Lin, Math. Comp., 2024], which is specifically designed to sidestep certain singularities in exchange energy evaluation, can expedite the finite-size convergence rate for the exact exchange energy across a range of insulators and semiconductors when compared to the regular and truncated Coulomb methods. This remains true even for two computationally cheaper versions of this new method, which we call non-SCF and split-SCF staggered mesh. Additionally, a sequence of numerical tests on simple solids showcases the staggered mesh method’s ability to improve convergence toward the thermodynamic limit for band gaps, bulk moduli, equilibrium lattice dimensions, energies, and phonon force constants.
ISSN:1549-9618
1549-9626
1549-9626
DOI:10.1021/acs.jctc.4c00771