Core-electron binding energies in atoms and monolayers adsorbed on metallic substrates

A Born-Haber cycle analysis of photoemission from atoms and monolayers adsorbed on metallic surfaces elucidates the effects of the substrate on the initial and final state contributions to measured core-electron binding energies. For rare gases both a dependence on the work function of the substrate and on the final state screening energy are identified. Depending on the relative magnitudes of the work function of the substrate and the ionization potential of the core-ionized atom, the screening charge may reside either in the substrate or on the adsorbate atom itself. Within the monolayer range, the coverage-dependence of the core-electron binding energy is shown to be largely a final-state effect. The Born-Haber cycle relating the Auger decay energy of an adsorbed core-ionized atom to that of a similar free atom is also presented. These formulations are tested using data for Xe adsorbed on Pd and Cs.