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Accelerated Molecular Dynamics Study of Z/E Isomerization of Azobenzene: Kramers’ Theory Validation

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Abstract

The reaction rate in a condensed phase is retarded by solvent friction and deviates from the transition state theory (TST) in a highly viscous solvent. The Z/E isomerization kinetics of 4-dimethylamino-4′-nitroazobenzene in solution have been experimentally analyzed in a wide range of pressure in our previous studies. Herein the non-TST behaviors of the rate constant were theoretically modelled by means of Kramers’ theory and its extensions and by molecular dynamics (MD) simulations. The Z/E isomerization takes place in milliseconds or longer and so is not reachable by normal MD simulations. The accelerated MD method was employed to simulate the rare events using a biased isomerization potential barrier.

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Authors and Affiliations

  1. Industrial Technology Center of Nagasaki, Ikeda, Omura, Nagasaki, 856-0026, Japan

    Yasuhiro Shigemitsu

  2. Gaduate School of Engineering, Nagasaki University, Nagasaki, 852-8521, Japan

    Yasuhiro Shigemitsu

  3. Department of Applied Chemistry, Oita University, Oita, 870-1124, Japan

    Yasushi Ohga

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  1. Yasuhiro Shigemitsu
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  2. Yasushi Ohga
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Correspondence to Yasuhiro Shigemitsu.

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Shigemitsu, Y., Ohga, Y. Accelerated Molecular Dynamics Study of Z/E Isomerization of Azobenzene: Kramers’ Theory Validation. J Solution Chem 43, 1746–1754 (2014). https://doi.org/10.1007/s10953-014-0237-5

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  • DOI: https://doi.org/10.1007/s10953-014-0237-5

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