Correlation effects in photoemission from adsorbates: Hydrogen on narrow-band metals.

Abstract

This paper deals with photoemission from a one-level atom adsorbed on a metal surface within the context of Anderson's Hamiltonian. The occupied part of the adsorbate density of states (DOS) is calculated by means of a many-electron approach that incorporates the following ingredients: (1) A neat separation between final-state interactions and initial (ground-state) effects. (2) The method (a Lehmann-type representation) leans heavily on the resolvent operator, R(z)=(z-H${)}^{\mathrm{\ensuremath{-}}1}$, which is obtained by expressing Dyson's equation in terms of the (N-1)-electron states (configurations) that diagonalize the hopping-free part of Anderson's Hamiltonian, thereby including the atomic correlation (U) in a nonperturbative way while expanding in powers of the hopping parameter (V). (3) By using blocking methods, the matrix elements of R are grouped into equivalent 4\ifmmode\times\else\texttimes\fi{}4 matrix blocks, with residual interactions, which are then put in correspondence with the sites of a rectangular lattice, thereby making the problem isomorphic to that of finding a noninteracting one-electron Green's function in the Wannier representation. (4) Renormalized perturbation theory, along with a series of convolution theorems due to Hugenholtz and Van Hove, allows one to develop a self-consistency equation that automatically takes into account an infinite number of configurations. The resulting DOS is compared with photoemission spectra from hydrogen adsorbed on tungsten (half-filled metal band) and nickel (almost full). Correlation effects turn out to produce peaks at the appropriate energies, so that an unusually good agreement is found despite the featureless, semielliptical DOS adopted for the metal. Only gross features of this quantity, such as width, center, and occupation of the band, seem to matter in a photoemission calculation.