Nonadiabatic corrections to electric current in molecular junction due to nuclear motion at the molecule-electrode interfaces

Vincent F. Kershaw, Daniel S. Kosov

Published 2018-03-09Version 1

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 nonequilibrium Green's functions. We separate time scales in the Green's functions on 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 Dyson 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 show that the nonadiabatic effects of nuclear motion of interfacial atoms generally reduce electrical conductivity in the resonance transport regime.