Effects of self-interaction corrections on the transport properties of phenyl-based molecular junctions

TL;DR

This paper investigates how self-interaction corrections in density functional theory impact the calculated transport properties of phenyl-based molecular junctions, showing that corrections generally reduce current by shifting molecular levels.

Contribution

It introduces a simple self-interaction correction scheme applied to molecular junction transport calculations, improving accuracy of level alignment and current predictions.

Findings

Corrections generally decrease the current in molecular junctions.

When junctions are insulating, corrections have minimal effect.

Self-interaction corrections improve the description of molecular level alignment.

Abstract

In transport calculations for molecular junctions based on density functional theory the choice of exchange and correlation functional may dramatically affect the results. In particular local and semi-local functionals tend to over-delocalize the molecular levels thus artificially increasing their broadening. In addition the same molecular levels are usually misplaced with respect to the Fermi level of the electrodes. These shortfalls are reminiscent of the inability of local functionals to describe Mott-Hubbard insulators, but they can be corrected with a simple and computationally undemanding self-interaction correction scheme. We apply such a scheme, as implemented in our transport code Smeagol, to a variety of phenyl-based molecular junctions attached to gold electrodes. In general the corrections reduce the current, since the resonant Kohn-Sham states of the molecule are shifted away from the contact Fermi level. In contrast, when the junction is already described as insulating by local exchange and correlation potentials, the corrections are minimal and the I-V is only weakly modified.