Using Non-covalent Interactions to Test Precision of Projector-Augmented Wave Data Sets

TL;DR

This paper demonstrates that analyzing non-covalent interactions in molecular dimers can reveal the origins of errors in PAW data sets and proposes a correction scheme to improve the accuracy of interaction energies.

Contribution

It introduces a novel approach using molecular dimers to diagnose and correct errors in PAW data sets, enhancing the precision of electronic structure calculations.

Findings

Interaction energy errors have short-range exponential and long-range electrostatic components.

A simple correction scheme significantly reduces long-range errors in hydrogen-bonded dimers.

The correction scheme decreases average interaction energy errors to less than half.

Abstract

The projector-augmented wave (PAW) method is one of the approaches that are widely used to approximately treat core electrons and thus to speed-up plane-wave basis set electronic structure calculations. However, PAW involves approximations and it is thus important to understand how they affect the results. Tests of precision of PAW data sets often use properties of isolated atoms or of atomic solids. While this is sufficient to identify problematic PAW data sets, little information has been gained to understand the origins of the errors and suggest ways to correct them. Here we show that interaction energies of molecular dimers are very useful not only to identify problematic PAW data sets but also to uncover the origin of the errors. Using dimers from the S22 and S66 test sets and other dimers we find that the error in the interaction energy is composed of a short range component with an exponential decay and a long range electrostatic part caused by error in the total charge density. We propose and evaluate a simple improvable scheme to correct the long range error and find that even in its simple and readily usable form, it is able to reduce the interaction energy errors to less than one half on average for hydrogen bonded dimers.