Author's School

Graduate School of Arts & Sciences

Author's Department/Program

Chemistry

Language

English (en)

Date of Award

10-23-2013

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Chair and Committee

Richard Mabbs

Abstract

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.

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.

Comments

Permanent URL: http://dx.doi.org/10.7936/K7862DGS

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