Modified superexchange model for electron tunneling across the terminated molecular wire

TL;DR

This paper develops a modified superexchange model for electron tunneling in molecular wires, deriving explicit formulas and comparing them with experimental data to better understand charge transfer mechanisms.

Contribution

It introduces a modified superexchange model with explicit analytic expressions for tunneling current, linking it to barrier models and experimental data.

Findings

Explicit expressions for nonresonant tunneling current are derived.

The model clarifies the role of energy levels in charge transmission.

Comparison with experimental data supports the model's validity.

Abstract

The explicit expressions for a nonresonant tunneling current mediated by the bridging units of the molecular wire embedded between the metallic electrodes, are derived. The specific regimes of the charge transmission controlled by nonresonant and resonant participation of terminal's energy levels are studied, and the role of energy position of delocalized orbitals in formation of a distant superexchange electrode-electrode coupling is clarified. The criteria for reduction of the superexchange model of charge tunneling to the flat barrier model are formulated and the parameters of the barrier model (energy gap and effective electron mass) are specified in the terms of inter-site coupling and energy distance from the Fermi level to the delocalized wire's HOMO (LUMO) level. Special attention is payed to derivation of explicit analytic expressions for the tunneling current using different approximations. It is shown that if terminal units play barrier's role in the charge transmission process, the best correspondence with the observed current-voltage characteristics is achieved with the simplest Gauss and the mean-value explicit forms. This is supported by comparison of the theory with experimental data concerning the current-voltage characteristics of $N-$alkanedithiol chain.