Gelin, Maxim F., and Kosov, Daniel S. (2021) A model for dynamical solvent control of molecular junction electronic properties. Journal of Chemical Physics, 154 (4). 044107.

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Abstract

Experimental measurements of electron transport properties of molecular junctions are often performed in solvents. Solvent–molecule coupling and physical properties of the solvent can be used as the external stimulus to control the electric current through a molecule. In this paper, we propose a model that includes dynamical effects of solvent–molecule interaction in non-equilibrium Green’s function calculations of the electric current. The solvent is considered as a macroscopic dipole moment that reorients stochastically and interacts with the electrons tunneling through the molecular junction. The Keldysh–Kadanoff–Baym equations for electronic Green’s functions are solved in the time domain with subsequent averaging over random realizations of rotational variables using the Furutsu–Novikov method for the exact closure of infinite hierarchy of stochastic correlation functions. The developed theory requires the use of wideband approximation as well as classical treatment of solvent degrees of freedom. The theory is applied to a model molecular junction. It is demonstrated that not only electrostatic interaction between molecular junction and solvent but also solvent viscosity can be used to control electrical properties of the junction. Alignment of the rotating dipole moment breaks the particle–hole symmetry of the transmission favoring either hole or electron transport channels depending upon the aligning potential.

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