Density functional description of long-range electron Coulomb interactions in bulk SnS

TL;DR

This paper introduces a high-throughput benchmarking method for exchange-correlation functionals in bulk SnS, revealing that gradient-dependent functionals outperform local density approximations in describing lattice properties.

Contribution

It proposes a novel benchmarking technique, classifies pseudopotentials based on lattice distortion effects, and suggests a strategy for learning exchange-correlation functionals considering long-range interactions.

Findings

Gradient-dependent functionals better describe lattice vectors than LDA.

Participation ratio correlates with structural distortion and hybridization.

A new strategy for functional development based on long-range potential analysis.

Abstract

A high-throughput benchmarking technique for testing the performance of different exchange-correlation functionals and pseudopotentials is proposed and applied to bulk SnS. It is shown that, contrary to the popular view that the local density approximation can best describe layered materials, a semilocal pseudopotential with a functional having a gradient dependence better described lattice vectors and `tetragonicity' of the lattice. We classify the pseudopotentials based on this value and show that the participation ratio of maximally localized Wannier functions follows the theory which states that more distorted structures have higher anti-bonding hybridization as stabilizing factor. In order to classify pseudopotentials, the local and nonlocal potential contributions to the dynamical Born effective charges are taken for each pseudopotential. Finally, a strategy is proposed for learning exchange-correlation functionals based on the distinction between short and long range parts of the Kohn-Sham potential.