Adsorption of small aromatic molecules on the (111) surfaces of noble metals: A density functional theory study with semiempirical corrections for dispersion effects

Abstract

The adsorption of benzene, thiophene, and pyridine on the (111) surface of gold and copper have been studied using density functional theory (DFT). Adsorption geometries and energies as well as the nature of bonding have been analyzed and compared to experimental results. Dispersion effects between neighboring molecules and between molecules and the surface have been taken into account via a semiempirical C6R−6 approach. The C6 coefficients for metal atoms have been deduced using both atomic properties and a hybrid QM:QM approach. Whereas the pure DFT calculations underestimate the adsorption energies significantly, a good agreement with experimental results is obtained using the DFT-D method based on the QM:QM hybrid approach.