Spectroscopy of transition metal dimers and trimers

The techniques of resonant two-photon ionization (R2PI) spectroscopy and laser induced fluorescence (LIF) spectroscopy were used to study several transition metal dimers and a transition metal trimer. This research was undertaken to elucidate the electronic structure of these small transition metal clusters. The construction of an LIF apparatus was undertaken to provide a complementary experiment to the existing R2PI instrument.; R2PI spectroscopy was used to study Ag{dollar}sb2{dollar}Au. One electronic band system was observed, assigning the molecule as belonging to the C{dollar}sb{lcub}rm 2v{rcub}{dollar} point group in both the ground and the excited electronic states. Vibrational progressions in both of the two totally symmetric (a{dollar}sb1){dollar} vibrational modes have been identified. Anharmonicities and lifetimes are also reported for the excited electronic state.; R2PI spectroscopy was used to reinvestigate Ni{dollar}sb2.{dollar} The improved cooling achieved in this study enabled reassignment of the ground electronic state and bond length. Seven new vibronic progressions were assigned, with spectroscopic constants determined for the excited states. A revised value for the binding energy and a value for the ionization energy of Ni{dollar}sb2{dollar} are given. Binding energies for the anion and cation are calculated.; Dispersed fluorescence studies of A1Ni, NiAu, and PtCu have been performed to obtain spectroscopic information about the ground and low-lying states of these molecules, and the results are compared to a ligand field plus spin-orbit calculation of the ground manifold of states. Vibrational frequencies for the ground state are reported for all three molecules.; Dispersed fluorescence spectroscopy was used to study jet-cooled AgAu and Pt{dollar}sb2{dollar} molecules. The observed fluorescence from AgAu yielded ground state information and an estimated bond length for the A state. The dispersed fluorescence data for Pt{dollar}sb2{dollar} yielded vibrational frequencies and anharmonicities of the ground and low-lying states. The Pt{dollar}sb2{dollar} data are compared to results obtained in a previous photoelectron spectroscopic study.; High resolution LIF studies of Au{dollar}sb2{dollar} and AlCa were performed using a cw ring dye laser for excitation. Ground and excited state bond lengths and symmetries were accurately determined, as well as a perturbation analysis performed for Au{dollar}sb2.{dollar}...