We investigate nonequilibrium two-electron transfer in a model redox system represented by a two-site extended Hubbard model and embedded in a dissipative environment. The influence of the electron-electron interactions and the coupling to a dissipative bosonic bath on the electron transfer is studied in different temperature regimes. At high temperatures, Marcus transfer rates are evaluated, and at low temperatures, we calculate equilibrium and nonequilibrium population probabilities of the donor and acceptor with the nonperturbative numerical renormalization group approach. We obtain the nonequilibrium dynamics of the system prepared in an initial state of two electrons at the donor site and identify conditions under which the electron transfer involves one concerted two-electron step or two sequential single-electron steps. The rates of the sequential transfer depend nonmonotonically on the difference between the intersite and on-site Coulomb interaction, which become renormalized in the presence of the bosonic bath. If this difference is much larger than the hopping matrix element, the temperature as well as the reorganization energy, simultaneous transfer of both electrons between donor and acceptor can be observed.

• Received 19 March 2008

DOI:https://doi.org/10.1103/PhysRevB.78.035434