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The 1s to 2π* resonances have been studied for CO strongly chemisorbed on Ni(100) and weakly chemisorbed on Cu(100) using high resolution X-ray absorption spectroscopy. We show that the spectra can be consistently described in terms of the local density of unoccupied 2π* electron states with the Fermi level obtained from corresponding X-ray photoelectron spectra. The core hole is demonstrated to induce large shifts in the unoccupied 2π* density of states.