The nonlocal correlation: A key to the solution of the CO adsorption puzzle

TL;DR

This paper demonstrates that incorporating nonlocal correlation via vdW-DF theory significantly improves the accuracy of predicting CO adsorption sites and energies on transition metal surfaces, addressing longstanding discrepancies.

Contribution

The study applies the vdW-DF nonlocal correlation functional to CO chemisorption, successfully resolving the adsorption puzzle and identifying the key length scale of correlation effects.

Findings

vdW-DF improves adsorption site predictions

Enhanced agreement with experimental adsorption energies

Identifies critical length scale for nonlocal correlation

Abstract

We study the chemisorption of CO molecule into sites of different coordination on (111) surfaces of late 4d and 5d transition metals. In an attempt to solve the well-known CO adsorption puzzle we have applied the relatively new vdW-DF theory of nonlocal correlation. The application of the vdW-DF functional in all considered cases improves or completely solves the discrepancies of the adsorption site preference and improves the value of the adsorption energy. By introducing a cutoff distance for nonlocal interaction we pinpoint the length scale at which the correlation plays a major role in the systems considered.