Detailed analysis of water structure in a solvent mediated electron tunneling mechanism

This work aims at describing the water structure characteristics that influence the electron transfer superexchange mechanism by explicitly calculating the solvent mediated conductance between the donor and acceptor in a generic pair. The method employed here is based on the non-equilibrium Green function formalism for calculating the conductance over solvent trajectories previously determined by molecular dynamics methods. A non-exponential dependence of the conductance is observed with respect to the distance between the donor and the acceptor. Local fluctuations of the solvent structure are responsible for the non-monotonic dependence, mainly due to the formation of solvent bridges that act as a molecular wire connecting the sites. This shortcutting phenomenon is observed for certain ranges of distances between the donor and acceptor in the pair. Charge on the sites strongly affects the local solvent structure and causes qualitative changes in the distance dependence of the tunneling probability.