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Computational Analysis of Solute–Solvent Coupling Magnitude in the Z/E Isomerization Reaction of Nitroazobenzene and Benzylideneanilines

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Abstract

The dynamic solvent effect often arises in solution reactions, where coupling between chemical reaction and solvent fluctuation plays a decisive role in the reaction kinetics. In this study, the Z/E isomerization reaction of nitoroazobenzene and benzylideneanilines in the ground state was computationally studied by molecular dynamics simulations. The non-equilibrium solvation effect was analyzed using two approaches: (1) metadynamics Gibbs energy surface exploration and (2) solvation Gibbs energy evaluation using a frozen solvation droplet model. The solute–solvent coupling parameter (Ccoupled) was estimated by the ratio of the solvent fluctuation Gibbs energy over the corresponding isomerization activation Gibbs energy. The results were discussed in comparison with the ones estimated by means of the analytical models based on a reaction–diffusion equation with a sink term. The second approach using a frozen solvation droplet reached qualitative agreement with the analytical models, while the first metadynamics approach failed. This is because the second approach explicitly considers the non-equilibrium solvation in the droplet, which consists of a solute at the reactant geometry immersed in the pre-organized solvents fitted with the solute at the transition state geometry.

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Acknowledgements

The authors thank to Prof. Mikhail Basilevsky (Russian Academy of Sciences) for his generous permission to use his program for evaluation of the parameter BW-C2. Helpful discussions with Professor Emeritus Tsutomu Asano (Oita University, Japan) and Prof. Noam Weinberg (University College of Fraser Valley, Canada) are greatly acknowledged. One of the authors (Y.S.) was financially supported by Grant-in-Aids for Scientific Research (C) (15K05434) from the Japan Society for the Promotion of Science.

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

    Yasuhiro Shigemitsu

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

    Yasuhiro Shigemitsu

  3. Faculty of Science and Technology, 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. Computational Analysis of Solute–Solvent Coupling Magnitude in the Z/E Isomerization Reaction of Nitroazobenzene and Benzylideneanilines. J Solution Chem 47, 127–139 (2018). https://doi.org/10.1007/s10953-018-0711-6

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