Towards an exact treatment of exchange and correlation in materials: Application to the "CO adsorption puzzle" and other systems

TL;DR

This paper proposes a cluster-based method to accurately correct exchange-correlation errors in materials, improving predictions for surface adsorption and bulk properties by leveraging high-quality quantum chemistry calculations.

Contribution

It introduces a universal, cluster-based correction approach for exchange-correlation functionals applicable to both bulk and defect systems, addressing limitations of current density functionals.

Findings

Improved prediction of CO adsorption sites on transition-metal surfaces.

Accurate calculation of bulk cohesive energies.

Demonstration of rapid convergence of xc correction with cluster size.

Abstract

It is shown that the errors of present-day exchange-correlation (xc) functionals are rather short ranged. For extended systems the correction can therefore be evaluated by analyzing properly chosen clusters and employing highest-quality quantum chemistry methods. The xc correction rapidly approaches a universal dependence with cluster size. The method is applicable to bulk systems as well as to defects in the bulk and at surfaces. It is demonstrated here for CO adsorption at transition-metal surfaces, where present-day xc functionals dramatically fail to predict the correct adsorption site, and for the crystal bulk cohesive energy.