Exact static linear response of excited states from ensemble density functional theory
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arXiv
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| Autori principali: | , |
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| Natura: | Preprint |
| Pubblicazione: |
2025
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| _version_ | 1866912603267137536 |
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| author | Dupuy, Lucien Fromager, Emmanuel |
| author_facet | Dupuy, Lucien Fromager, Emmanuel |
| contents | Following a recent work [E. Fromager, J. Phys. Chem. A 2025, 129, 4, 1143-1155] on the ensemble density functional theory (DFT) of excited electronic energy levels, we derive in this paper the ensuing static linear response theory, thus allowing for an in-principle exact evaluation of excited-state density-density linear response functions in a completely frequency-independent setting. Once individual-state components of the inverse ensemble linear response function have been introduced, a working Dyson-type equation naturally emerges for each state, individually. By considering the zero-weight limit of the theory, which infinitesimally deviates from standard Kohn--Sham DFT, exact excited-state corrections to ground-state linear response DFT can be identified. They involve the first-order weight derivatives of the ensemble Hartree-exchange-correlation (Hxc) potential and kernel, thus confirming the importance in ensemble DFT of both weight and density-functional derivatives of the ensemble Hxc energy functional. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2506_16363 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Exact static linear response of excited states from ensemble density functional theory Dupuy, Lucien Fromager, Emmanuel Chemical Physics Following a recent work [E. Fromager, J. Phys. Chem. A 2025, 129, 4, 1143-1155] on the ensemble density functional theory (DFT) of excited electronic energy levels, we derive in this paper the ensuing static linear response theory, thus allowing for an in-principle exact evaluation of excited-state density-density linear response functions in a completely frequency-independent setting. Once individual-state components of the inverse ensemble linear response function have been introduced, a working Dyson-type equation naturally emerges for each state, individually. By considering the zero-weight limit of the theory, which infinitesimally deviates from standard Kohn--Sham DFT, exact excited-state corrections to ground-state linear response DFT can be identified. They involve the first-order weight derivatives of the ensemble Hartree-exchange-correlation (Hxc) potential and kernel, thus confirming the importance in ensemble DFT of both weight and density-functional derivatives of the ensemble Hxc energy functional. |
| title | Exact static linear response of excited states from ensemble density functional theory |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.16363 |