Exchange correlation potentials from full configuration interaction in a Slater orbital basis

Soumi Tribedi; Duy-Khoi Dang; Bikash Kanungo; Vikram Gavini; Paul M Zimmerman

doi:10.1063/5.0157942

Exchange correlation potentials from full configuration interaction in a Slater orbital basis

J Chem Phys. 2023 Aug 7;159(5):054106. doi: 10.1063/5.0157942.

Authors

Soumi Tribedi^{1

2}, Duy-Khoi Dang¹, Bikash Kanungo³, Vikram Gavini^{3

4}, Paul M Zimmerman¹

Affiliations

¹ Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.
² Michigan Institute for Data Science, University of Michigan, Ann Arbor, Michigan 48109, USA.
³ Department of Mechanical Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA.
⁴ Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA.

PMID: 37530106
DOI: 10.1063/5.0157942

Abstract

Ryabinkin-Kohut-Staroverov (RKS) theory builds a bridge between wave function theory and density functional theory by using quantities from the former to produce accurate exchange-correlation potentials needed by the latter. In this work, the RKS method is developed and tested alongside Slater atomic orbital basis functions for the first time. To evaluate this approach, full configuration interaction computations in the Slater orbital basis are employed to give quality input to RKS, allowing full correlation to be present along with correct nuclei cusps and asymptotic decay of the wavefunction. SlaterRKS is shown to be an efficient algorithm to arrive at exchange-correlation potentials without unphysical artifacts in moderately-sized basis sets. Furthermore, enforcement of the nuclear cusp conditions will be shown to be vital for the success of the Slater-basis RKS method. Examples of weakly and strongly correlated molecular systems will demonstrate the main features of SlaterRKS.