Journal of Physical Chemistry B, Vol.104, No.16, 3804-3807, 2000
Phenomenological approach to thermally assisted tunneling
Most of low-temperature reactions proceed faster than would be predicted by an Arrhenius-type extrapolation from the high-temperature regions. The definitions of low- and high-temperature regions are quite conditional, depending strongly on the properties of the host matrix for a given reactant. The transition from the low-temperature region to the high-temperature region, manifested by a break in an Arrhenius plot, is accompanied by the marked decrease of reaction dispersivity. In the low-temperature region, the specific reaction rates depend on time. For a time-dependent specific reaction rate, using the concept of the 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, in the Gamov picture for a simple rectangular barrier of constant height, is described in terms of a distribution function for the tunneling distance, related directly to the distribution function of logarithms of lifetimes calculable from the kinetic equation with a time-dependent specific reaction rate. In the high-temperature region, classical kinetics with a constant specific reaction rate provides a good approximation. This is rationalized in terms of the stochastic model of reaction kinetics in the renewing environment. In the model, the structural relaxation of the host matrix is included by imposing upon the static disorder model the additional assumption that at random the reinitialization occurs. The reinitialization consists of random reassignment of guest hopping rates with the values having the same initial distribution. Therefore, the breaks in Arrhenius plots might be taken to be an indication of the onset of thermal assistance for tunneling, not necessarily of the change from quantum mechanical under barrier transition to thermally activated over barrier transition. As an example, the reactions of excess electrons in aqueous systems are discussed.