Geminate Recombination in the Presence of Scavengers: The New Vision of the Old Problem

Abstract

A geminate reaction between and reactants affected by the bulk reaction between and scavengers is discussed. The exact solution of the problem obtained recently for randomly walking reactant (excess electron) is compared with the superposition approximation commonly used to interpret experimental data. Distinctions related to the important role of time correlations between geminate and bulk reactions are analyzed. The largest deviations exponentially growing in time are observed for geminate reaction rate in the presence of scavengers. It is shown that superposition approximation can decrease essentially the ultimate probability of geminate recombination. The difference is great enough to lead to qualitatively incorrect description of the experiment even at small concentration of scavengers. This, in turn, may give rise to considerable errors in the determination of geminate pair parameters or, alternatively, to the wrong information about bulk kinetics of electron scavenging.