Auxiliary many-body wavefunctions for TDDFRT electronic excited states: Consequences for the representation of molecular electronic transitions
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arXiv
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| Hauptverfasser: | , , |
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| Format: | Preprint |
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2021
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| _version_ | 1866917096642838528 |
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| author | Morere, Jérémy Monino, Enzo Etienne, Thibaud |
| author_facet | Morere, Jérémy Monino, Enzo Etienne, Thibaud |
| contents | This contribution reports the study of a set of molecular electronic-structure reorganization representations related to light-induced electronic transitions, modeled in the framework of time-dependent density-functional response theory. More precisely, the work related in this paper deals with the consequences, for the electronic transitions natural-orbital characterization, that are inherent to the use of auxiliary many-body wavefunctions constructed a posteriori and assigned to excited states - since time-dependent density-functional response theory does not provide excited state ansatze in its native formulation. Three types of such auxiliary many-body wavefunctions are studied, and the structure and spectral properties of the relevant matrices (the one-electron reduced difference and transition density matrices) is discussed and compared with the native equation-of-motion time-dependent density functional response theory picture of an electronic transition - we see for instance that within this framework the detachment and attachment density matrices can be derived without diagonalizing the one-body reduced difference density matrix. The common ''departure/arrival'' wavefunction-based representations of electronic transitions are also extensively discussed. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2104_13616 |
| institution | arXiv |
| publishDate | 2021 |
| record_format | arxiv |
| spellingShingle | Auxiliary many-body wavefunctions for TDDFRT electronic excited states: Consequences for the representation of molecular electronic transitions Morere, Jérémy Monino, Enzo Etienne, Thibaud Chemical Physics This contribution reports the study of a set of molecular electronic-structure reorganization representations related to light-induced electronic transitions, modeled in the framework of time-dependent density-functional response theory. More precisely, the work related in this paper deals with the consequences, for the electronic transitions natural-orbital characterization, that are inherent to the use of auxiliary many-body wavefunctions constructed a posteriori and assigned to excited states - since time-dependent density-functional response theory does not provide excited state ansatze in its native formulation. Three types of such auxiliary many-body wavefunctions are studied, and the structure and spectral properties of the relevant matrices (the one-electron reduced difference and transition density matrices) is discussed and compared with the native equation-of-motion time-dependent density functional response theory picture of an electronic transition - we see for instance that within this framework the detachment and attachment density matrices can be derived without diagonalizing the one-body reduced difference density matrix. The common ''departure/arrival'' wavefunction-based representations of electronic transitions are also extensively discussed. |
| title | Auxiliary many-body wavefunctions for TDDFRT electronic excited states: Consequences for the representation of molecular electronic transitions |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2104.13616 |