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Reversible dynamics and the macroscopic rate law for a solvable Kolmogorov system: The three bakers' reaction
Authors:Yves Elskens  Raymond Kapral
Affiliation:(1) Service de Chimie Physique II, Université Libre de Bruxelles, Campus Plaine, C.P. 231 1050 Bruxelles, Belgium;(2) Department of Chemistry, University of Toronto, M5S 1A1 Toronto, Ontario, Canada
Abstract:
We investigate a piecewise linear (area-preserving) mapT describing two coupled baker transformations on two squares, with coupling parameter 0lescles1. The resulting dynamical system is Kolmogorov for anycne0. For rational values ofc, we construct a generating partition on whichT induces a Markov chain. This Markov structure is used to discuss the decay of correlation functions: exponential decay is found for a class of functions related to the partition. Explicit results are given forc=2–n. The macroscopic analog of our model is a leaking process between two (badly) stirred containers: according to the Markov analysis, the corresponding progress variable decays exponentially, but the rate coefficients characterizing this decay are not those determined from the one-way flux across the cell boundary. The validity of the macroscopic rate law is discussed.
Keywords:Kolmogorov system  Markov chain  rate laws  correlation function decay  relaxation process
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