Non-adiabatic corrections to electric current in molecular junctions due to nuclear motion at the molecule-electrode interfaces

Kershaw, Vincent F.;Kosov, Daniel S.

Abstract

We present quantum electron transport theory that incorporates dynamical effects of motion of atoms on electrode-molecule interfaces in the calculations of the electric current. The theory is based on non-equilibrium Green’s functions. We separate time scales in the Green’s functions as fast relative time and slow central time. The derivative with respect to the central time serves as a small parameter in the theory. We solve the real-time Kadanoff-Baym equations for molecular Green’s functions using Wigner representation and keep terms up to the second order with respect to the central time derivatives. Molecular Green’s functions and consequently the electric current are expressed as functions of molecular junction coordinates as well as velocities and accelerations of molecule-electrode interface nuclei. We apply the theory to model a molecular system and study the effects of non-adiabatic nuclear motion on molecular junction conductivity.

Journal

Journal of Chemical Physics

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Volume

149

ISBN/ISSN

1089-7690

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Publisher

American Institute of Physics

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DOI

10.1063/1.5028333