Nonlinear charge transport in redox molecular junctions: a Marcus perspective

TL;DR

This paper develops an analytical model for nonlinear charge transport in redox molecular junctions based on Marcus theory, predicting phenomena like conduction, rectification, and negative differential resistance with temperature-dependent behaviors.

Contribution

It provides the first analytical solution for molecular conduction in the Marcus regime and explores nonlinear transport features without detailed electronic structure assumptions.

Findings

Conduction, rectification, and negative differential resistance can occur in redox junctions.

Transport behaviors depend on the interplay of multiple conduction channels.

Model predictions align with experimentally observed temperature dependences.

Abstract

Redox molecular junctions are molecular conduction junctions that involve more than one oxidation state of the molecular bridge. This property is derived from the ability of the molecule to transiently localize transmitting electrons, implying relatively weak molecule-leads coupling and, in many cases, the validity of the Marcus theory of electron transfer. Here we study the implications of this property on the non-linear transport properties of such junctions. We obtain an analytical solution of the integral equations that describe molecular conduction in the Marcus kinetic regime and use it in different physical limits to predict some important features of nonlinear transport in metal-molecule-metal junctions. In particular, conduction, rectification and negative differential resistance can be obtained in different regimes of interplay between two different conduction channels associated with different localization properties of the excess molecular charge, without specific assumptions about the electronic structure of the molecular bridge. The predicted behaviors show temperature dependences typically observed in the experiment. The validity of the proposed model and ways to test its predictions and implement the implied control strategies are discussed