Theoretical approaches in adsorption: alkali adatom investigations

We discuss how different properties at surfaces could require for different theoretical treatments within the first-principles density functional theory. Energies and structures are accurately determined by adopting the supercell geometry. Surface states are more conveniently described by the Green function embedding approach, which is able to take into account a truly semi-infinite solid and hence real continuous spectra. In this way a detailed analysis of discrete and resonant states is provided. We mainly describe the embedding method and provide examples to compare the two approaches. We focus next on the structural and electronic properties of alkali adatoms. The adsorption structure of Na/Cu(001) at low coverages is calculated within the supercell geometry motivated by the results of the Cambridge group on surface diffusion by 3He spin echo scattering. The dispersion, energy, effective mass, and width of surface (quantum well and image) states of alkali atoms on Cu(111) are worked out by the embedding approach and compared with experiments.