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In this paper the first resonant photoemission and partial electron yield studies of free clusters are presented. The resonant photoemission spectra of free argon clusters have been recorded with excitation energies determined from the cluster X-ray absorption spectrum near the Ar 2p ionization threshold. The decay of 2p⁻¹4s and 2p⁻¹3d cluster surface and “bulk” excited states has been investigated in detail. The combination of resonant photoemission and partial electron yield methods has allowed a selective probing of the electronic and geometric structure, yielding new results concerning the interplay between the energy of the excited states, their orbital character and the local atomic coordination. These new results demonstrate the power of resonant core level spectroscopy when applied to free clusters, as well as the advantages of free clusters for the studies of the bulk and surface energetics of nanoscale …