Une nouvelle théorie de la cinétique des réactions radical-radical

Abstract

Radical recombination reactions are of central importance in radiation chemistry. In general such reactions are slower than diffusion-controlled because of the radical spins. The rate constant is corrected by a multiplicative spin statistical factor, which represents the probability that the radicals encounter one another in a reactive state. However, this method does not account for the possibility that the reactivity of a pair may recover following an unreactive encounter, for example by spin relaxation or by a coherent evolution of the spin function. In this paper we show how the spin statistical factor can be corrected for the recovery of reactivity. The new theory covers a large range of mechanisms for the recovery of reactivity, and gives simple analytical results. Both steady-state and transient solutions are presented and the former are tested against experiment for the reaction between the hydrated electron and oxygen, and for the magnetic field effect on the rate constant of an elementary reaction.