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Stochastic transition states: Reaction geometry amidst noise

J. Chem. Phys. 123, 204102 (2005); doi:10.1063/1.2109827

Published 18 November 2005

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Thomas Bartsch and T. Uzer
Center for Nonlinear Science and School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332-0430

Rigoberto Hernandez
Center for Nonlinear Science and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0300
Classical transition state theory (TST) is the cornerstone of reaction-rate theory. It postulates a partition of phase space into reactant and product regions, which are separated by a dividing surface that reactive trajectories must cross. In order not to overestimate the reaction rate, the dynamics must be free of recrossings of the dividing surface. This no-recrossing rule is difficult (and sometimes impossible) to enforce, however, when a chemical reaction takes place in a fluctuating environment such as a liquid. High-accuracy approximations to the rate are well known when the solvent forces are treated using stochastic representations, though again, exact no-recrossing surfaces have not been available. To generalize the exact limit of TST to reactive systems driven by noise, we introduce a time-dependent dividing surface that is stochastically moving in phase space, such that it is crossed once and only once by each transition path. ©2005 American Institute of Physics
History: Received 7 July 2005; accepted 14 September 2005; published 18 November 2005
Permalink: http://link.aip.org/link/?JCPSA6/123/204102/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.20.Db
    Transition state theory and statistical theories of rate constants (chemical kinetics)
  • 82.20.Hf
    Product distribution in chemical kinetics
  • 82.20.Uv
    Stochastic theories of rate constants in chemical kinetics
  • 82.20.Nk
    Classical theories of reactions and/or energy transfer in chemical kinetics
  • 82.30.-b
    Specific chemical reactions; reaction mechanisms
  • YEAR: 2005

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ISSN:
0021-9606 (print)   1089-7690 (online)
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