First-principles scheme for spectral adjustment in nanoscale transport

TL;DR

This paper introduces a first-principles spectral adjustment method for nanoscale transport calculations that corrects the HOMO-LUMO gap, improving agreement with experiments and matching sophisticated approaches like GW.

Contribution

The paper presents a general ab-initio approach for spectral correction in nanoscale transport, addressing the underestimation of energy gaps and validating it against advanced methods.

Findings

Corrects HOMO-LUMO gap for better experimental agreement

Lorentzian fitting underestimates conductance compared to the proposed method

Method aligns well with GW calculations and explains conductance histogram features

Abstract

We implement a general method for correcting the low-bias transport properties of nanoscale systems within an ab-initio methodology based on linear combinations of atomic orbitals. We show how the typical problem of an underestimated HOMO-LUMO gap can be corrected, leading to quantitative and qualitative agreement with experiments. We show that an alternative method based on calculating the position of the relevant transport resonances and fitting them to Lorentzians can significantly underestimate the conductance and does not accurately reproduce the electron transmission coefficient between resonances. We compare this simple method in an ideal system of a benzene molecule coupled to featureless leads to more sophisticated approaches such as $GW$ and find a rather good agreement between both. We also present results for a benzene-dithiolate molecule between gold leads, where we study different coupling configurations for straight and tilted molecules, and show that this method yields the observed evolution of two-dimensional conductance histograms. We also explain the presence of low conductance zones in such histograms by taking into account different coupling configurations.