Electron tunneling between two electrodes mediated by a molecular wire containing a redox center

We derive an explicit expression for the quantum conductivity of a molecular wire containing a redox center, which is embedded in an electrochemical environment. The redox center interacts with the solvent, and the average over the solvent configurations is performed numerically. Explicit calculations have been performed for a chain of three atoms. When the redox center interacts strongly with neighboring electronic levels, the current-potential curves show interesting features like rectification, current plateaus and negative differential resistance. Electronic spectroscopy of intermediate states can be performed at constant small bias by varying the electrochemical potential of the wire.