Modelling the Kohn-Sham potential for molecular dissociation with orbital-independent functionals: a proof of principle
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| Format: | Preprint |
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2024
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| _version_ | 1866912017155096576 |
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| author | Giarrusso, Sara Agostini, Federica |
| author_facet | Giarrusso, Sara Agostini, Federica |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2408_06038 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Modelling the Kohn-Sham potential for molecular dissociation with orbital-independent functionals: a proof of principle Giarrusso, Sara Agostini, Federica Chemical Physics Strongly Correlated Electrons 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. |
| title | Modelling the Kohn-Sham potential for molecular dissociation with orbital-independent functionals: a proof of principle |
| topic | Chemical Physics Strongly Correlated Electrons |
| url | https://arxiv.org/abs/2408.06038 |