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Nonlinear dynamical effects on reaction rates in thermally fluctuating environments

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タイトル: Nonlinear dynamical effects on reaction rates in thermally fluctuating environments
著者: Kawai, Shinnosuke 著作を一覧する
Komatsuzaki, Tamiki 著作を一覧する
発行日: 2010年 7月21日
出版者: Royal Society of Chemistry
誌名: Physical Chemistry Chemical Physics
巻: 12
号: 27
開始ページ: 7636
終了ページ: 7647
出版社 DOI: 10.1039/b922596j
抄録: A framework to calculate the rate constants of condensed phase chemical reactions of manybody systems is presented without relying on the concept of transition state. The theory is based on a framework we developed recently adopting a multidimensional underdamped Langevin equation in the region of rank-one saddle. The theory provides a reaction coordinate expressed as an analytical nonlinear functional of the position coordinates and velocities of the system (solute), the friction constants, and the random force of the environment (solvent). Up to moderately high temperature, the sign of the reaction coordinate can determine the final destination of the reaction in a thermally fluctuating media, irrespective of what values the other (nonreactive) coordinates may take. In this paper, it is shown that the reaction probability is analytically derived as the probability of the reaction coordinate being positive, and that the integration with the Boltzmann distribution of the initial conditions leads to the exact reaction rate constant when the local equilibrium holds and the quantum effect is negligible. Because of analytical nature of the theory taking into account all nonlinear effects and their combination with fluctuation and dissipation, the theory naturally provides us with the firm mathematical foundation of the origin of the reactivity of the reaction in a fluctuating media.
Rights: Phys. Chem. Chem. Phys., 2010, 12, 7636-7647 - Reproduced by permission of the PCCP Owner Societies
資料タイプ: article (author version)
出現コレクション:雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

提供者: 河合 信之輔


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