Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C

Jonathon Witte; Jeffrey B Neaton; Martin Head-Gordon

doi:10.1063/1.4986962

Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C

J Chem Phys. 2017 Jun 21;146(23):234105. doi: 10.1063/1.4986962.

Authors

Jonathon Witte¹, Jeffrey B Neaton², Martin Head-Gordon¹

Affiliations

¹ Department of Chemistry, University of California, Berkeley, California 94720, USA.
² Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.

PMID: 28641421
DOI: 10.1063/1.4986962

Abstract

With the aim of mitigating the basis set error in density functional theory (DFT) calculations employing local basis sets, we herein develop two empirical corrections for basis set superposition error (BSSE) in the def2-SVPD basis, a basis which-when stripped of BSSE-is capable of providing near-complete-basis DFT results for non-covalent interactions. Specifically, we adapt the existing pairwise geometrical counterpoise (gCP) approach to the def2-SVPD basis, and we develop a beyond-pairwise approach, DFT-C, which we parameterize across a small set of intermolecular interactions. Both gCP and DFT-C are evaluated against the traditional Boys-Bernardi counterpoise correction across a set of 3402 non-covalent binding energies and isomerization energies. We find that the DFT-C method represents a significant improvement over gCP, particularly for non-covalently-interacting molecular clusters. Moreover, DFT-C is transferable among density functionals and can be combined with existing functionals-such as B97M-V-to recover large-basis results at a fraction of the cost.