Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited⊥
作者： Barry Moore , Haitao Sun , Niranjan Govind , Karol Kowalski , Jochen Autschbach
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摘要: Criteria to assess charge-transfer (CT) and CT-like character of electronic excitations are examined. Time-dependent density functional theory (TDDFT) calculations with non-hybrid, hybrid, tuned long-range corrected (LC) functionals compared coupled-cluster (CC) benchmarks. The test set comprises an organic CT complex, two push-pull donor-acceptor chromophores, a cyanine dye, several polycyclic aromatic hydrocarbons. Proper is easily identified. Excitations significant changes upon excitation within regions close spatial proximity can also be diagnosed. For such excitations, the use LC in TDDFT sometimes leads dramatic improvements singlet energies, similar proper CT. It shown that do not have characteristics physical charge transfer, may obtained for right reasons. triplet energies underestimated all systems, often severely. candidates, singlet-triplet (S/T) separation from negative non-hybrid positive functional. cyanine, S/T systematically too large TDDFT, leading better error compensation energy
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