Embedding approach to the isolated adsorbate.

Abstract

An embedding method is proposed, based upon Green-function matching, for calculating the electronic properties of an isolated adsorbate. The self-consistent single-particle Schr\odinger equation is solved in a localized region containing the adsorbate and that part of the substrate mainly perturbed by it. The extended substrate is taken into account exactly by an effective embedding potential. The advantages of the method for the adsorption problem are discussed and tested by a calculation of the electronic properties of isolated Si and N adatoms on Al, modeled as jellium. In the former case excellent agreement is found with the results previously computed by other methods, in the latter, not previously investigated by a first-principles approach, the ioniclike character of the bond is seen in the calculated charge densities and densities of states. Finally the problem of the lack of screening due to the presence of an adatom on a simple metal surface is estimated by the generalized phase-shift theory. This effect turns out to be an important contribution to the atom-surface interaction energies, and it is corrected to first order by the use of the grand-canonical energy functional. \textcopyright{} 1996 The American Physical Society.