title: Chemically intuitive indices for charge-transfer excitation based on SAC-CI and TD-DFT calculations.
abstract: A recently proposed charge-transfer (CT) index and some related quantities aimed to the description of CT excitations in push-pull donor-acceptor model systems were computed in vacuum and in ethanol by the direct symmetry-adapted cluster-configuration interaction (SAC-CI) method including solvent effects by means of the nonequilibrium state-specific approach. The effects of both solvation and electron correlations on these quantities were found to be significant. The present results are also in line with previous time-dependent (TD) density functional theory calculations and they demonstrate that SAC-CI provides a description of the excitation character close to that of TD-PBE0. Indeed, CT indices evaluated by the SAC-CI and TD-PBE0 would be useful in the field of materials chemistry, for the design and development of novel molecular materials.
authors.affiliation: Institute for Molecular Science and Research Center for Computational Science, 38 Nishigo-naka, Myodaiji, Okazaki, 444-8585, Japan; Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University Katsura, Kyoto, 615-8520, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Ehara
authors.forename: Ryoichi
authors.initials: R
authors.lastname: Fukuda
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
mesh_terms: D000465:Algorithms; D011108:Polymers / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D011108:Polymers; C041325:polyphenylene sulfide
keywords: charge-transfer; electron correlation; electron density; excited states; solvent effect