TY - JOUR

T1 - Dynamics of reactions involving diffusive barrier crossing

AU - Schulten, Klaus

AU - Schulten, Zan

AU - Szabo, Attila

N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.

PY - 1981

Y1 - 1981

N2 - We develop a first passage time description for the kinetics of reactions involving diffusive barrier crossing in a bistable (and also in a more general) potential, a situation realized, for example, in some photoisomerization processes. In case the reactant is in thermal equilibrium, the first passage times account well for the reaction dynamics as shown by comparison with exact numerical calculations. A simple integral expression for the rate constants is presented. For a case involving a reactant initially far off equilibrium, a two relaxation time description for the particle number N(t) is derived and compared with the results of an "exact" calculation. This description results from a knowledge of N(t=0), N(t=0), ∫0∞dt N(t), i.e., the first passage time, and ∫0∞dt t N(t).

AB - We develop a first passage time description for the kinetics of reactions involving diffusive barrier crossing in a bistable (and also in a more general) potential, a situation realized, for example, in some photoisomerization processes. In case the reactant is in thermal equilibrium, the first passage times account well for the reaction dynamics as shown by comparison with exact numerical calculations. A simple integral expression for the rate constants is presented. For a case involving a reactant initially far off equilibrium, a two relaxation time description for the particle number N(t) is derived and compared with the results of an "exact" calculation. This description results from a knowledge of N(t=0), N(t=0), ∫0∞dt N(t), i.e., the first passage time, and ∫0∞dt t N(t).

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U2 - 10.1063/1.441684

DO - 10.1063/1.441684

M3 - Article

AN - SCOPUS:0001069331

SN - 0021-9606

VL - 74

SP - 4426

EP - 4432

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

IS - 8

ER -