Photoelectron Imaging of Iodide Centered Alkyl Halide Cluster Anions

<p>This dissertation presents results from cluster anion photodetachment experiments of the solvated iodide anion as a means of investigating electron molecule interaction. Due to the localization of the excess charge on the iodine atom, these experiments proceed analogously to electron scattering experiments, in that exposure to sufficient photon energy detaches the electron, which may or may not interact with the target molecule before being detected. Such interactions are related to temporary electron capture into the σ* orbital of the target molecule.</p><p>This dissertation begins with an analysis of the previously published I−·CH3X: X = I, Br, Cl) photodetachment results. These results are used to gain insight on electron molecule interaction. The results are compared with ab initio calculations as well as the electron scattering literature. The bulk of this dissertation discusses the role of the target molecule in cluster anion photodetachment. The insights developed from the I−·CH3X cluster anions are applied to I−·C2H5X: X = I, Br, Cl) and I−·CH2X2: X = I, Br, Cl) detachment. The experimental cluster anion photoelectron angular distribution trends deviate somewhat from the ab initio calculations and experimental electron scattering data. A discussion follows, wherein these deviations are attributed to the incident electron angular momentum and lifetime broadening of the σ* resonance. Furthermore, a spherical square well model is developed to aid in the discussion.

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2013

Author dc:creator

• Lasinski, Joshua S.

Contributors dc:contributor

• Richard Mabbs

• Dissociative Electron Attachment
• Electron Scattering
• Photodetachment
• Spectroscopy
• Velocity Map Imaging
• Chemistry

Language dc:language

English (en)

DOI

https://doi.org/10.7936/K7862DGS

OAI identifier oai:identifier

oai:openscholarship.wustl.edu:etd-2187