Bridge mediated two-electron transfer reactions: on the influence of intersite Coulomb interactions

Donor-acceptor two-electron transfer (TET) mediated by a linear molecular bridge is described theoretically. The particular case is considered where the TET takes place in the presence of a strong electronic intersite coupling within the bridge and against the background of fast vibrational relaxation processes. For such a situation the coarse-grained description of bridge-assisted electron transfer in molecular systems can be utilized [Petrov et al., J. Phys. Chem. B 106, 3092 (2002)]. In the present case it leads to kinetic equations and rate expression for TET reactions. Our recent treatment of completely nonadiabtic TET reactions [Petrov et al., J. Chem. Phys. 120, 4441 (2004)] including a reduction to single-exponential kinetics (with overall transfer rate K(TET)) is generalized here to the case of strong intrabridge coupling and the presence of intersite Coulomb interactions. The dependence of K(TET) on the bridge length which is determined by a separate stepwise and concerted contribution is discussed in detail. It is found that the intersite Coulomb interaction favors the TET if the donor and the acceptor are uncharged in their completely reduced states (with two excess electrons present).