Ultraviolet photoelectron spectroscopy of copper clusters

Using a new magnetically focused time-of-flight photoelectron spectrometer, the ultraviolet photoelectron spectra (UPS) of mass-selected negative copper clusters have been measured at photon energy of 4.66 eV for all clusters in the range from 6 through 41 copper atoms. These UPS data provide the first detailed probe of the 4s valence band structure of such medium size negative copper clusters, and extend previous approximate measures of the electron affinity of the corresponding neutral species. The results are in accord with the predictions of the ellipsoidal shell model for monovalent metal clusters. In particular, clusters 8, 20, and 40 (which correspond to spherical shell closings in this simple model) are found to have unusually low electron affinities and large HOMO–LUMO gaps. Subshell closings at 14 and 34 also appear special in this new UPS data.