The mass spectra of copper(I) doped neon and argon clusters obtained in a time-of-flight apparatus are presented. Electronic structure calculations with density functional theory reveal that the first closed shell of Cu +Ne n complexes consists of 12 atoms with icosahedral geometry, whereas for Cu +Ar n complexes, six atoms form an octahedral structure. These results are in accord with the mass spectra, which show a substantial decrease in the intensities for the clusters with n>12 neon atoms and n>6 argon atoms. For both inert gas atoms the calculated geometry of Cu +Rg 4 aggregates is found planar and not tetrahedral as it is expected for a cation with a spherical symmetry.
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