Local and nonlocal effects in the core ionization of metal-molecule adsorbates and cluster systems

An nb initio Green's function comparative study of the Cls ionization of Pd CO and Pd3CO clusters has revealed distinct nonlocal effects in the spectru m of Pd3CO. A good agreement with the experimental Cls spectrum of CO adsor bed on small Pd particles is achieved. A breakdown of individual charge tra nsfer (CT) satellites associated with the basic PdCO unit of Pd3CO has been discovered. This breakdown is due to the coupling of the individual local CT states to a manifold of nonlocal double metal-adsorbate excitations and leads to a broadening of the giant satellites in adsorbate core-hole spectr a.