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Generalized Huber kinetics for nonlinear rate processes in disordered systems: Nonlinear analogs of stretched exponential
Phys. Rev. E 57, 6497 – Published 1 June, 1998
DOI: https://doi.org/10.1103/PhysRevE.57.6497
Abstract
This paper deals with one-variable nonlinear rate processes occurring in disordered systems. A general stochastic approach is introduced for these processes based on the following assumptions. The total rate coefficient is made up of the additive contributions of a large number of individual reaction channels. These contributions are random functions of time and their stochastic properties are characterized by a functional random point process. Exact analytical expressions for the time dependence of the average concentration are derived by using a characteristic functional technique. These expressions are valid for systems with both dynamic and static disorder and are nonlinear analogs of the general kinetic law derived by Huber [Phys. Rev. B 31, 6070 (1985); Phys. Rev. E 53, 6544 (1996)] for linear rate processes in systems with static disorder. For independent rate processes with static disorder and a self-similar distribution of reaction channels we derive a nonlinear analog of the stretched exponential. A closed analytic expression of the nonlinear stretched exponential is given in terms of Fox’s functions. As expected, when the reaction order of the process is one, the nonlinear kinetic law reduces to a stretched exponential with a scaling exponent characterizing the self-similar distribution of the individual reaction channels. For nonlinear processes the tail of the averaged kinetic curve is self-similar and obeys a scaling law with a negative power law. Surprisingly, the scaling exponent of the tail depends only on the reaction order of the process and is independent of the scaling exponent that characterizes the self-similar distribution of the individual channels. We examine the possibilities of experimental evaluation of the statistical distribution of the total rate coefficient: The moments of different orders of the rate coefficient can be evaluated from the time derivatives of the survival function.
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