| The interaction between light and electrons is one of the most widely studied physical phenomena, and a primary means of characterizing the properties of condensed matter systems. Many experimental techniques have been developed which make use of light to probe materials in bulk, on substrates and in the gas phase. Photoelectron spectroscopy (PES) is one such technique, in which monochromatic photons are used to photodetach electrons whose kinetic energy is then measured. Through energy conservation, the difference between the energy of the incoming photons and outgoing electrons is then equal to the difference in energy between the initial and final state of the molecule from which the electron was ejected. This difference is defined as the binding energy of the electron, a spectrum of the number of electrons versus their binding energy can be plotted. With sufficient resolution, PES can be used to determine both the electronic and vibrational structure of clusters, however the price of this versatility is that it is difficult to interpret PES without complementary theoretical investigation. In this thesis we first present background information on PES theory and our ab initio calculations, and then delve into our use of theoretical techniques to interpret the PES spectra of three different types of transition metal clusters. (Abstract shortened by UMI.). |
