Determination of the theoretical rate constants for the reduction reactions of lanthanide ions by hydrated electrons

The mechanism of the reduction reaction of lanthanide(III) ions by hydrated electrons in polar solvents has been investigated. The theoretical rate constants for the reaction of hydrated electrons with a number of lanthanide ions have been calculated using the energy gap laws of the charge shift reaction(D+−A→D−A+) and compared with experimental values. With these results, we have explained the large difference of the reaction rates of lanthanide ions with hydrated electrons, which depend upon the kind of lanthanide ion. The calculated results agree almost quantitatively with the experimental values.