Photoelectron Spectroscopy Studies of Anionic Clusters: CO2 Reduction, Metal Hydrides, Low Barrier Hydrogen Bonding, and Solvent Stabilization
Graham, Jacob David
MetadataShow full item record
Anion photoelectron spectroscopy was combined with theoretical studies to examine the electronic and geometric properties of negative ions. A diverse range of negative ions were studied including metal hydrides, complexes with a CO2 moiety and systems containing strong, low barrier hydrogen bonds. In particular, the intermolecular bonding in the above negative ions is a central theme of this thesis. In certain cases, the additional electron occupies a molecular bonding orbital that stabilizes the entire anionic complex. This scenario is identified in both the organic complex (Quinoline-CO2)- and aluminum hydride AlH4- where the removal of an electron changes these species into van der Waals complexes. In other cases, ionic bonding is found to be the dominant interaction in a negative ion complex. Examples of such systems studied include (Cobalt-Pyridine-CO2)- and dimers of deprotonated acids that form low barrier hydrogen bonds such as the formate-formic acid anion. Selected dissociation energies in the above described complexes are examined. Additionally, the stabilizing effect of water on several unstable anions is studied. These include hydrated forms of formaldehyde, acetaldehyde and acetone anions.