English

Modelling the Kohn-Sham potential for molecular dissociation with orbital-independent functionals: a proof of principle

Chemical Physics 2024-09-09 v3 Strongly Correlated Electrons

Abstract

We model the Hartree-exchange-correlation potential of Kohn-Sham density-functional theory adopting a novel strategy inspired by the strictly-correlated-electrons limit and relying on the exact decomposition of the potential based on the exact factorization formalism. Starting with accurate density and conditional potential for a one-dimensional model of a stretched heteronuclear molecule, we provide a proof-of-principle example of an approximation that accurately reproduces the step of the exact Kohn-Sham potential without resorting to the Kohn-Sham orbitals, virtual or occupied. We also test our strategy using the approximate conditional potentials corresponding to the strictly-correlated-electron and the exact-exchange functionals. The results are encouraging in that the initial approximations are modified in the qualitatively correct way: decreasing correlation in the former and increasing it in the latter.

Keywords

Cite

@article{arxiv.2408.06038,
  title  = {Modelling the Kohn-Sham potential for molecular dissociation with orbital-independent functionals: a proof of principle},
  author = {Sara Giarrusso and Federica Agostini},
  journal= {arXiv preprint arXiv:2408.06038},
  year   = {2024}
}