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Dynamic pathways to mediate reactions buried in thermal fluctuations. I. Time-dependent normal form theory for multidimensional Langevin equation
| Title: | Dynamic pathways to mediate reactions buried in thermal fluctuations. I. Time-dependent normal form theory for multidimensional Langevin equation |
| Authors: | Kawai, Shinnosuke Browse this author | | Komatsuzaki, Tamiki Browse this author |
| Keywords: | fluctuations | | friction | | random processes | | reaction kinetics theory | | solvent effects | | stochastic processes | | thermal noise |
| Issue Date: | 14-Dec-2009 |
| Publisher: | American Institute of Physics |
| Journal Title: | Journal of Chemical Physics |
| Volume: | 131 |
| Issue: | 22 |
| Start Page: | 224505 |
| Publisher DOI: | 10.1063/1.3268621 |
| PMID: | 20001055 |
| Abstract: | We present a novel theory which enables us to explore the mechanism of reaction selectivity and robust functions in complex systems persisting under thermal fluctuation. The theory constructs a nonlinear coordinate transformation so that the equation of motion for the new reaction coordinate is independent of the other nonreactive coordinates in the presence of thermal fluctuation. In this article we suppose that reacting systems subject to thermal noise are described by a multidimensional Langevin equation without a priori assumption for the form of potential. The reaction coordinate is composed not only of all the coordinates and velocities associated with the system (solute) but also of the random force exerted by the environment (solvent) with friction constants. The sign of the reaction coordinate at any instantaneous moment in the region of a saddle determines the fate of the reaction, i.e., whether the reaction will proceed through to the products or go back to the reactants. By assuming the statistical properties of the random force, one can know a priori a well-defined boundary of the reaction which separates the full position-velocity space in the saddle region into mainly reactive and mainly nonreactive regions even under thermal fluctuation. The analytical expression of the reaction coordinate provides the firm foundation on the mechanism of how and why reaction proceeds in thermal fluctuating environments. |
| Rights: | Copyright 2009 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 131, 224505 (2009) and may be found at https://dx.doi.org/10.1063/1.3268621 |
| Type: | article |
| URI: | http://hdl.handle.net/2115/42520 |
| Appears in Collections: | 電子科学研究所 (Research Institute for Electronic Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 河合 信之輔
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