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Tytuł:
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Fast Nonadiabatic Molecular Dynamics via Spin-Flip Time-Dependent Density-Functional Tight-Binding Approach: Application to Nonradiative Relaxation of Tetraphenylethylene with Locked Aromatic Rings.
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Autorzy:
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Uratani H; Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan.
Morioka T; Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan.
Yoshikawa T; Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan.; Waseda Research Institute for Science and Engineering (WISE), 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan.
Nakai H; Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan.; Waseda Research Institute for Science and Engineering (WISE), 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan.; Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8245, Japan.
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Źródło:
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Journal of chemical theory and computation [J Chem Theory Comput] 2020 Dec 08; Vol. 16 (12), pp. 7299-7313. Date of Electronic Publication: 2020 Nov 16.
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Typ publikacji:
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Journal Article
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Język:
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English
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Imprint Name(s):
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Original Publication: Washington, D.C. : American Chemical Society, c2005-
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Entry Date(s):
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Date Created: 20201116 Date Completed: 20201208 Latest Revision: 20201214
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Update Code:
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20240105
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DOI:
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10.1021/acs.jctc.0c00936
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PMID:
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33197192
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Nonadiabatic dynamics around conical intersections between ground and excited states are crucial to understand excited-state phenomena in complex chemical systems. With this background in mind, we present an approach combining fewest-switches trajectory surface hopping and spin-flip (SF) time-dependent (TD) density-functional tight binding (DFTB), which is a simplified version of SF-TD density functional theory (DFT) with semiempirical parametrizations, for computationally efficient nonadiabatic molecular dynamics simulations. The estimated computational time of the SF-TD-DFTB approach is several orders of magnitude lower than that of SF-TD-DFT. In addition, the proposed method reproduces the time scales and quantum yields in photoisomerization reactions of azobenzene at a level comparable with conventional ab initio approaches, demonstrating reasonable accuracy. Finally, we report a practical application of the developed technique to explore the nonradiative relaxation processes of tetraphenylethylene and its derivative with torsionally locked aromatic rings and discuss the effect of locking the rings on the excited-state lifetime.
