Size-dependent transformation of energy structure in free tin clusters studied by photoelectron spectroscopy

Free nanoscale tin clusters in the average size range of a few tens up to ∼500 atoms are studied by means of valence and core-level photoelectron spectroscopy. A self-consistent picture arises from comparison of the work functions derived from the 4d core-level spectra, the experimental ionization energies extracted from the 5p valence spectra, and the expectations from the metallic sphere model for the clusters. The present studies demonstrate that the 4d core-level energy changes are a sensitive probe of the metal-to-semiconductor transition in the size range under investigation.