Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C
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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Jun 20, 2017
- Source ID
- 10.1063/1.4986962
Entities
People
- Jeffrey B. Neaton
- Jonathon Witte
- Martin Head-Gordon
Organizations
- Lawrence Berkeley National Laboratory
- United States Department of Defense
- United States Department of Energy
- Yusuf Hamied Department of Chemistry