Benchmark density functional theory calculations for nano-scale conductance

TL;DR

This paper benchmarks density functional theory methods for nano-scale conductance, comparing plane wave and atomic orbital basis sets across five molecular junctions to evaluate accuracy and convergence.

Contribution

It provides a systematic comparison of DFT-based transmission calculations using different basis sets and establishes convergence criteria for accurate nano-scale conductance predictions.

Findings

Siesta transmission functions converge to plane-wave results with larger basis sets

Double-zeta plus polarization basis set achieves quantitative agreement

Systematic downward shift observed in Siesta transmission functions

Abstract

We present a set of benchmark calculations for the Kohn-Sham elastic transmission function of five representative single-molecule junctions. The transmission functions are calculated using two different density functional theory (DFT) methods, namely an ultrasoft pseudopotential plane wave code in combination with maximally localized Wannier functions, and the norm-conserving pseudopotential code Siesta which applies an atomic orbital basis set. For all systems we find that the Siesta transmission functions converge toward the plane-wave result as the Siesta basis is enlarged. Overall, we find that an atomic basis with double-zeta and polarization is sufficient (and in some cases even necessary) to ensure quantitative agreement with the plane-wave calculation. We observe a systematic down shift of the Siesta transmission functions relative to the plane-wave results. The effect diminishes as the atomic orbital basis is enlarged, however, the convergence can be rather slow.