Phenomenological interpretation of kinetics with time-dependent specific reaction rates

Abstract

Abstract Specific reaction rates depend on time for reactions proceeding on time scales comparable to or shorter than those of internal rearrangements in the reaction system renewing the environment of reactants. For a time-dependent specific reaction rate, k ( t ), using the concept of energy profile along the reaction path, one finds the potential energy barrier separating reactants from products to evolve in time during the reaction course. This evolution is described in terms of a distribution function related directly to the distribution function of logarithms of lifetimes calculable from the kinetic equations with k ( t ). This advanced approach is compared with that in which the kinetic equations with k ( t ) are interpreted in terms of superposition of classical reaction patterns.