Bridge mediated two-electron transfer reactions: analysis of stepwise and concerted pathways

A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D-(-)BA with the product state DBA-(-) results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate KTET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D-B-A, DB-(-)A, D-BA-, and DB-A-, KTET is obtained as a sum of the rates KTET(step) and KTET(sup). The first rate describes stepwise TET originated by transitions of a single electron. It starts at D-(-)BA and reaches DBA-(-) via the intermediate state D-BA-. These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D-(-)BA to DBA-(-) defines KTET(sup). An analytic dependence of KTET(step) and KTET(sup) on the number of bridging units is presented and different regimes of D-A TET are studied.