ROLE OF DIFFUSION IN PHOTOINDUCED ELECTRON-TRANSFER ON A MICELLE SURFACE - THEORETICAL AND MONTE-CARLO INVESTIGATIONS

A detailed theoretical treatment of donor-acceptor photoinduced forwar d electron transfer and back transfer (geminate recombination) for mol ecules diffusing on a micelle surface is presented. Expressions are gi ven for the time-dependent survival probabilities of both the excited- state donor and the charge-transfer state formed by forward electron t ransfer. Incorporation of diffusion has a pronounced effect on the kin etics of both the forward and the back transfer, and the amount of gem inate recombination depends critically on the Coulombic potential betw een the ions. Ion spatial distributions as a function of time are pres ented and used to discuss the possibility of achieving long-term ion s eparation. The validity of the theory is demonstrated by comparison to Monte Carlo simulations of the problem, and the perfect agreement obt ained confirms the accuracy of the theoretical derivation.