Photoionization spectroscopy of ionic metal dimers: LiCu and LiAg

Abstract

Electronic spectra are reported for the heteronuclear metal dimers LiCu and LiAg, with resonant one-color two-photon ionization (R2PI). The dimers are produced in a pulsed supersonic molecular beam by laser vaporization of either a copper or silver rod coated with a thin film of vacuum deposited lithium metal. A total of twelve excited electronic states for LiCu and seven for LiAg are observed. Analysis of the vibrational progressions yields ground and excited state vibrational frequencies and dissociation energies for both LiCu and LiAg. In addition, selected vibronic bands are rotationally resolved. This data, together with that obtained by Morse and co-workers for LiCu [J. Chem. Phys. (to be published)], gives bond lengths for LiCu and LiAg (r0″=2.26 and 2.41 Å, respectively). The bond lengths for LiCu and LiAg are significantly shorter than expected by comparison to the homonuclear diatomics Li2 and Cu2 or Ag2. Dissociation energies in the heteronuclear dimers are also much greater than the mean of the corresponding homonuclear dimer values. These trends indicate that ionic character plays a leading role in the ground-state bonding.