Abstract
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 S2 state.
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Acknowledgments
This work was supported by the National Natural Science Foundation of China (grants 10874234, 90923003, 10804015) and the Fundamental Research Funds for the Central Universities (grant no: DL12BB19).
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Li, Y., Shi, Y., Chen, M. et al. Molecular modeling of two-photon absorption and third-order nonlinearities of polymethine dyes for all-optical switching. J Mol Model 18, 4141–4149 (2012). https://doi.org/10.1007/s00894-012-1407-2
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DOI: https://doi.org/10.1007/s00894-012-1407-2