CO adsorption on the Pt(111) surface: a comparison of a gradient corrected functional and a hybrid functional

TL;DR

This study compares gradient corrected and hybrid functionals in DFT calculations of CO adsorption on Pt(111), revealing that the choice of functional significantly affects predicted adsorption sites.

Contribution

It demonstrates how different density functionals influence the predicted preferred adsorption sites of CO on Pt(111), highlighting the importance of functional selection in surface chemistry modeling.

Findings

Perdew-Wang functional favors fcc site, consistent with previous studies.

B3LYP functional favors top site, differing from Perdew-Wang.

The change in adsorption site preference is linked to differences in molecular orbital splitting.

Abstract

The adsorption of CO on the Pt(111) surface in a root3 x root3 pattern has been studied with the gradient corrected functional of Perdew and Wang and the B3LYP hybrid functional. A slab which is periodic in two dimensions is used to model the system. The Perdew-Wang functional incorrectly gives the fcc site as the most favorable adsorption site, in accord with a set of previous studies. The B3LYP functional gives the top site as the preferred site. This confirms results from cluster studies where it was suggested that the different splitting, dependent on the functional, between highest occupied and lowest unoccupied molecular orbital, could be the reason for this change of the adsorption site. This is supported by an analysis based on the projected density of states and the Mulliken population.