Abstract
Free ion yields from geminate ion pairs formed after photoinduced electron transfer are measured by the transient photocurrent method in three moderately polar solvents. Photoexcited 9,10-dicyanoanthracene (DCA) is used as the electron acceptor and alkyl-substituted benzenes as donors. It was found that, generally, there is no significant change in free ion yield as the temperature is increased. On the basis of a theoretical model developed under Collins−Kimball boundary conditions, several factors are analyzed, including dielectric constants and viscosities of solvents, initial separation distance distribution of geminate ion pairs, and temperature-induced changes in recombination rates. By comparing escape probabilities of geminate ion pairs calculated at different initial formation and recombination/separation distances with measured free ion yields, we show that free ions are mainly produced from the solvent-separated ion pairs that are initially formed after electron transfer quenching of photoexcite...
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