Auxiliary many-body wavefunctions for TDDFRT electronic excited states: Consequences for the representation of molecular electronic transitions

Abstract

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.