Simplified Tuning of Long-Range Corrected Density Functionals for Use in Symmetry-Adapted Perturbation Theory

10 June 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Long considered a failure, second-order symmetry-adapted perturbation theory (SAPT) based on Kohn-Sham orbitals, or SAPT(KS), can been resurrected for semiquantitative purposes using long-range corrected (LRC) density functionals whose asymptotic behavior is adjusted separately for each monomer. As in other contexts, correct asymptotic behavior can be enforced via "optimal tuning" of LRC functionals, based on the ionization energy theorem, but the tuning procedure is tedious, expensive for large systems, and comes with a troubling dependence on system size. Here, we show that essentially identical results are obtained using an automated tuning procedure based on the size of the exchange hole, making tuned "SAPT(wKS)" fast and convenient. In conjunction with SAPT-based methods that sidestep second-order dispersion, this procedure achieves benchmark-quality interaction energies, along with the usual SAPT energy decomposition, without the hassle of system-specific tuning.

Keywords

intermolecular interactions
noncovalent binding energies

Supplementary materials

Title
Description
Actions
Title
wGDD-SAPT-SuppInfo
Description
Actions

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