First-Principles Analysis of Molecular Conduction Using Quantum Chemistry Software

TL;DR

This paper introduces a parameter-free, first-principles method combining quantum chemistry software with NEGF formalism to analyze electronic transport in molecular wires, bridging chemistry and transport physics.

Contribution

It couples standard quantum chemistry software with NEGF for a simple, transparent analysis of molecular conduction, applicable to different contact types.

Findings

Successfully modeled I-V characteristics of molecular wires

Demonstrated the method's ability to distinguish conduction regimes

Provided detailed electron density and voltage profiles

Abstract

We present a rigorous and computationally efficient method to do a parameter-free analysis of molecular wires connected to contacts. The self-consistent field approach is coupled with Non-equilibrium Green's Function (NEGF) formalism to describe electronic transport under an applied bias. Standard quantum chemistry software is used to calculate the self-consistent field using density functional theory (DFT). Such close coupling to standard quantum chemistry software not only makes the procedure simple to implement but also makes the relation between the I-V characteristics and the chemistry of the molecule more obvious. We use our method to interpolate between two extreme examples of transport through a molecular wire connected to gold (111) contacts: band conduction in a metallic (gold) nanowire, and resonant conduction through broadened, quasidiscrete levels of a phenyl dithiol molecule. We obtain several quantities of interest like I-V characteristic, electron density and voltage drop along the molecule.