The interaction of adsorbates with metal surfaces is discussed. It is shown that the evanescent charge density produced by occupied sp derived surface states yields a considerable contribution to the Pauli repulsion experienced by adsorbate particles with a closed-shell electronic structure, e.g. rare-gases or molecules such as H-2 or N-2 For rare-gases this results in a reduction of the binding energy in the presence of occupied surface states, for molecules this gives rise to an additional contribution to the dissociation barrier. Suitable surface dopants are able to depopulate surface states and thereby to reduce the dissociation barrier. Such dopants can substantially promote catalytic reactions in which the dissociation from the gas phase or a physisorbed precursor is the rate limiting step. In contrast to closed-shell systems the bonding interaction for metal adsorbates on metal substrates is enhanced by occupied surface states. This leads to an extra diffusion barrier at steps, because the surface state amplitude drops to zero at upper step edges. The additional step-edge barrier, which is a kinetic hindrance for layer-by-layer growth, can be reduced by surface dopants depopulating the corresponding surface state. Such dopants promote layer-by-layer growth and act therefore as surfactants. It is concluded that the effect of promoters in catalysis and of surfactants in metal epitaxy is in part due to the same basic mechanism, namely the depopulation of surface states.
