Theory of Nonadiabatic Electron Transitions in Symmetrical
Two-Center Tunnel Electrochemical Contact

A. M. Kuznetsov^z

Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia

Received January 10, 2007

Abstact—Passage of current through two-center bridge contact is studied theoretically for a nonadiabatic
mechanism of electron transfer. General expressions for steady-state current as a function of overvoltage and
bias voltage are obtained. For a symmetrical contact, a simple approximate expression is derived for current in
the limit when electron transfer between bridge redox-groups is the slow stage. It is shown that the current as a
function of overvoltage passes through a maximum near the equilibrium potential. The shape of the maximum
does not depend on the medium reorganization energy.

Key words: tunnel contact, two-center bridge molecule, electron transfer, transition probability

DOI: 10.1134/S1023193507120014

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