Calculation of the work function with a local basis set

TL;DR

This paper presents a simple scheme to accurately compute the work function using local basis sets by adding extra basis functions in the vacuum region, achieving results comparable to experimental data.

Contribution

It introduces a novel method to improve work function calculations with local basis sets by incorporating additional vacuum basis functions.

Findings

Good agreement with experimental data

Effective for various surfaces

Simple to implement in existing codes

Abstract

Electronic structure codes usually allow to calculate the work function as a part of the theoretical description of surfaces and processes such as adsorption thereon. This requires a proper calculation of the electrostatic potential in all regions of space, which is apparently straightforward to achieve with plane wave basis sets, but more difficult with local basis sets. To overcome this, a relatively simple scheme is proposed to accurately compute the work function when a local basis set is used, by having some additional basis functions in the vacuum. Tests on various surfaces demonstrate that a very good agreement with experimental and other theoretical data can be achieved.