Molecular Adsorption on Metal Surfaces with a van der Waals Density Functional

Abstract: The adsorption of 1,4-benzenediamine (BDA) on the Au(111) surface and azobenzene on the Ag(111) surface is investigated using density functional theory (DFT) with a non-local density functional (vdW-DF) and a semi-local Perdew-Burke-Ernzerhof (PBE) functional. For BDA on Au(111), the inclusion of London dispersion interactions not only dramatically enhances the molecule-substrate binding, resulting in adsorption energies consistent with experimental results, but also significantly alters the BDA binding geometry. For azobenzene on Ag(111), the vdW-DF produces superior adsorption energies compared to those obtained with other dispersion corrected DFT approaches. These results provide evidence for the applicability of the vdW-DF method and serves as a practical benchmark for the investigation of molecules adsorbed on noble metal surfaces.