| Anion photoelectron spectroscopy is employed to study semiconductor clusters and solvated species. The electronic structure of III-V semiconductor clusters have been studied in an effort to understand how their electronic structure changes as a function of size from discreet molecular states to bulk band structure. Several low-lying electronic states and spin orbit splittings have been determined for group III-V diatomics, AlP, GaP, InP, and GaAs. Photoelectron angular distributions allowed us to identify overlapping electronic states.; Vibrationally resolved photoelectron spectra of Aluminum Phosphide (Al xPy−) and GaX−, GaX2−, Ga2X−, and Ga2X3− (X = P,As) clusters were measured at various photodetachment wavelengths. Electron affinities, term energies, and vibrational frequencies for the ground and excited electronic states of the neutral clusters have been obtained. The assignments of excited electronic states were aided by ab initio calculations, as well as measurements of photoelectron angular distributions.; Other system studied include I2−· (CO2) Van der Waals clusters and solvated transition state precursors. The I2−· (CO2) experiment yields size-dependent vertical and adiabatic detachment energies for the formation of the ground state and low-lying valence-excited states of the neutral cluster. Vertical detachment energies are successively blue-shifted with increasing cluster size, indicating a stronger stabilization of the anionic cluster relative to the neutral counterpart. Very interesting ion-solvent interactions are observed for I2−· (CO2) clusters. Photoelectron spectra of clusters of the type XHX− (M) (X = Br, I) where M = H2O, HBr and HI, provide information about solvent induced changes to the transition state of a bimolecular reaction. |
