Master equation and Fokker-Planck equation: Comparison of entropy and of rate constants

被引:11
作者
Gaveau, B
Moreau, M
Toth, J
机构
[1] UNIV PARIS 06,PHYS THEOR LIQUIDES LAB,F-75252 PARIS 05,FRANCE
[2] UNIV AGR SCI,DEPT COMP SCI,H-2103 GODOLLO,HUNGARY
关键词
master equation; Fokker-Planck equation; rate constants; entropy;
D O I
10.1023/A:1007362811930
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
A usual approximation of the master equation is provided by the Fokker-Planck equation. For chemical systems with one species, we prove generally that the prediction of the rate constant of the metastable state given by the Master equation and the Fokker-Planck approximation differ exponentially with respect to the size of the system. We show that this is related to the fact that the entropy of the metastable state is not described correctly by the Fokker-Planck equation. We prove that the rate given by the Fokker-Planck equation overestimates that rate given by the Master equation.
引用
收藏
页码:101 / 115
页数:15
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