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论文类型：期刊论文

发表时间：2012-09-01

发表刊物：JOURNAL OF MOLECULAR MODELING

收录刊物：SCIE、Scopus

卷号：18

期号：9

页面范围：4141-4149

ISSN号：1610-2940

关键字：Two-photon absorption; Charge transfer; Transition density; Charge difference density

摘要：Stimulated by a recent experimental report [Hales JM et al. (2010) Science 327:1485-1488], two-photon absorption and third-order optical nonlinearities of selenopyrylium- and bis(dioxaborine)-terminated polymethine dyes (called SE-7C and DOB-9C) used for all-optical switching were investigated theoretically with time-dependent DFT (TD-DFT) and response theory as well as visualized real-space analysis. The calculated results for the first hyperpolarizability and second hyperpolarizability demonstrated that the two molecules both have large third-order optical nonlinearities. Using real-space analysis, we were able to visually determine that in the one-photon absorption (OPA) process, the first singlet excited state of SE-7C and DOB-9C is an intramolecular charge transfer (ICT) excited state with strong absorption, while the second excited state of these dyes (also termed the "ICT state") shows weak absorption. However, in the two-photon absorption (TPA) process, a larger TPA absorption cross-section was predicted for the second excited state. In this paper, we describe the properties of the S2 excited state, incorporating charge transfer and the transition moment, via real-space analysis, which was very important for understanding the TPA characteristics of the S-2 state.