Note on the Theory of Diffusion Controlled Reactions : Application to Photodissociation in Solution

The theory of diffusion controlled reactions has been reconsidered in the light of modern transport theory, and it has been concluded that the use of the Smoluchowski equation is valid for most problems of usual interest. The probability of reaction has been calculated for two molecules initially separated by a distance r′, in the presence of a third reactant present in uniform concentration. The resulting formulas have been used to discuss the quantum yields of photodissociation of Br2, Br3—, and I3— in aqueous solution. The dependence on temperature and wavelength can be qualitatively accounted for.