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The modified superexchange model shows wide possibilities to clarify the mechanism of formation of a tunneling current through terminated molecular wire. The model has no inherent rigid restrictions of the standard superexchange model. This allows to obtain the analytical expressions for the analysis of the current–voltage characteristics of the wire, in which the voltage bias does not destroy the delocalzation of molecular orbitals belonging to the interior region of the wire. The conditions under which the modified superexchange model leads to the results that follow from the Simmons model of tunneling through a rectangular barrier, or the McConnell model of superexchange tunneling, are presented. The mechanism by which the wire's terminal units with the biased energies that do or do not resonate with the Fermi‐levels of the electrodes control the current, is clarified. Using an example of a molecular wire with a regular bridging alkane chain, it is shown that the model predicts current–voltage characteristics that are in good agreement with the experimental data on the attenuation of the tunneling current with an increase of the chain length.

Modified Superexchange Model for Electron Tunneling Across the Terminated Molecular Wire