Photodissociation spectroscopy of Ag-4(+)(N-2)(m), m=0-4

We have determined photodissociation spectra of Ag-4(+)(N-2)(m=0-4) in the photon energy range from 2.1 to 3.75 eV. The cluster complexes were generat ed by laser vaporization and their absolute photodissociation cross section s were measured in depletion using a modified reflectron time-of-flight mas s spectrometer. The band spectra show significant nonmonotonic variations w ith increasing N-2 coverage. The experimental data are contrasted with quan tum chemical calculations of ground and electronically excited states using density functional as well as post-Hartree-Fock methods. Experiment and th eory are in qualitative agreement allowing tentative assignment of the depl etion spectra and insight into the relevant bonding interactions. (C) 2000 American Institute of Physics. [S0021-9606(00)01137-5].