PHOTOELECTRON-SPECTROSCOPY AND ELECTRONIC-STRUCTURE OF CLUSTERS OF THE GROUP-V ELEMENTS .1. DIMERS

The HeI (584 Å) high resolution photoelectron spectra of As 2+, Sb2+, and Bi2 + have been obtained with a high temperature molecular beam source. A pure As2 beam was produced by evaporating Cu3 As. Sb 2 was generated as a mixture with the atoms and tetramers by evaporating the pure element, while Bi2 was generated as a mixture with only the atoms from the pure element. Vibrational structure was well resolved for the As2+ spectrum. Spectroscopic constants were derived and reported for the related ionic states. In addition, we have carried out relativistic complete active space self-consistent field followed by multireference single + double configuration interaction calculations on these dimers both for the neutral ground states and the related ionic states. The agreements between the calculated and experimentally derived spectroscopic constants were fairly good, although the calculations tended to underestimate consistently the strength of the bonding in these heavy homonuclear diatomics. © 1990 American Institute of Physics.