HUSCAP logo Hokkaido Univ. logo

Hokkaido University Collection of Scholarly and Academic Papers >
Research Institute for Electronic Science >
Peer-reviewed Journal Articles, etc >

Why and how do systems react in thermally fluctuating environments?

Files in This Item:
PCCP13-48_21217-21229.pdf745.66 kBPDFView/Open
Please use this identifier to cite or link to this item:http://hdl.handle.net/2115/50277

Title: Why and how do systems react in thermally fluctuating environments?
Authors: Kawai, Shinnosuke Browse this author
Komatsuzaki, Tamiki Browse this author →KAKEN DB
Issue Date: 28-Dec-2011
Publisher: Royal Society of Chemistry
Journal Title: Physical Chemistry Chemical Physics
Volume: 13
Issue: 48
Start Page: 21217
End Page: 21229
Publisher DOI: 10.1039/c1cp22504a
PMID: 22048614
Abstract: Many chemical reactions, including those of biological importance, take place in thermally fluctuating environments. Compared to isolated systems, there arise markedly different features due to the effects of energy dissipation through friction and stochastic driving by random forces reflecting the fluctuation of the environment. Investigation of how robustly the system reacts under the influence of thermal fluctuation, and elucidating the role of thermal fluctuation in the reaction are significant subjects in the study of chemical reactions. In this article, we start with overviewing the generalized Langevin equation (GLE), which has long been used and continues to be a powerful tool to describe a system surrounded by a thermal environment. It has been also generalized further to treat a nonstationary environment, in which the conventional fluctuation-dissipation theorem no longer holds. Then, within the framework of the Langevin equation we present a method recently developed to extract a new reaction coordinate that is decoupled from all the other coordinates in the region of a rank-one saddle linking the reactant and the product. The reaction coordinate is buried in nonlinear couplings among the original coordinates under the influence of stochastic random force. It was ensured that the sign of this new reaction coordinate (= a nonlinear functional of the original coordinates, velocities, friction, and random force) at any instant is sufficient to determine in which region, the reactant or the product, the system finally arrives. We also discuss how one can extend the method to extract such a coordinate from the GLE framework in stationary and nonstationary environments, where memory effects exist in dynamics of the reaction.
Rights: Phys. Chem. Chem. Phys., 2011, 13, 21217-21229 - Reproduced by permission of the PCCP Owner Societies
Type: article (author version)
URI: http://hdl.handle.net/2115/50277
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)

Submitter: 河合 信之輔

Export metadata:

OAI-PMH ( junii2 , jpcoar_1.0 )

MathJax is now OFF:


 

 - Hokkaido University