| A number of negatively charged cluster ion systems have been studied using the technique of negative ion photoelectron spectroscopy. In this technique, a mass selected beam of negative ions is crossed with a fixed frequency laser beam, and the resultant photodetached electrons are energy analyzed. Three types of cluster anions are discussed in this thesis: metal cluster anions, solvated electron clusters, and anion-molecule complexes.; Photoelectron spectra of the homogeneous alkali metal cluster anions: {dollar}rm Nasbsp{lcub}n=2-5{rcub}{lcub}-{rcub},{dollar} {dollar}rm Ksbsp{lcub}n=2-19{rcub}{lcub}-{rcub},{dollar} {dollar}rm Rbsbsp{lcub}n=2-3{rcub}{lcub}-{rcub},{dollar} and {dollar}rm Cssbsp{lcub}n=2-3{rcub}{lcub}-{rcub},{dollar} as well as the heterogeneous alkali dimers and trimers: NaK{dollar}sp-,{dollar} KRb{dollar}sp-,{dollar} RbCs{dollar}sp-,{dollar} KCs{dollar}sp-,{dollar} Na{dollar}sb2{dollar}K{dollar}sp-,{dollar} and K{dollar}sb2{dollar}Cs{dollar}sp-{dollar} have been obtained. The spectra of all dimer anion species have been assigned. All the spectra are highly structured, with the structure arising from low lying electronic states of the clusters. Electron affinities, vertical detachment energies, and electronic state energy splittings for several series of metal clusters have been determined from the spectra. This allows variations of electronic properties and electronic structure to be traced as a function of cluster size. In addition, the production of large metal and semiconductor cluster ions has been studied, and their applications to material science considered.; The photoelectron spectra of water cluster anions, {dollar}rm (Hsb2O)sbsp{lcub}n{rcub}{lcub}-{rcub},{dollar} n = 2, 6, 7, 11-69 provide vertical detachment energies (VDE's), which were found to increase smoothly with increasing cluster size. A plot of the VDE's vs. n{dollar}sp{lcub}-1/3{rcub}{dollar} for n {dollar}geq{dollar} 11 is linear and extrapolates to a VDE({dollar}infty){dollar} which is very near the photoemission threshold for condensed phase hydrated electrons. The linear extrapolation of this data to the corresponding bulk phase property suggests that these gas phase cluster anions are closely related to the condensed phase hydrated electron.; The anion-molecule complexes studied are illustrated via {dollar}rm NOsp-(Hsb2O)sb{lcub}n=1,2{rcub}.{dollar} The photoelectron spectra show evidence for an NO{dollar}sp-{dollar} spectral manifold shifted to higher electron binding energies while the absence of vibrational structure is due to the broadening of individual vibrational transitions. Adiabatic electron affinities and anion-single solvent dissociation (sequential solvation) energies were determined from the spectra. |
