Methyl Halide Cluster Anion Photoelectron Spectra and Angular Distributions as a Probe of Electron-Molecule Interactions

This dissertation describes the development of a method for studying electron &ndash molecule interactions using cluster anion photodetachment. Photodetachment from an atomic centered cluster anion produces a free electron and a residual neutral species at a geometry near that of the unperturbed neutral ground state. Evidence of the free electron &ndash molecule interactions, manifested in the photoelectron spectra and angular distributions, are elucidated through comparison to photodetachment data from the unsolvated atomic anion in question. Results are presented from number of monosolvated anion studies, including I<super>&minus</super>&middot CH₃I, I<super>&minus</super>&middot CH₃Br, I<super>&minus</super>&middot CH₃Cl and Cl<super>&minus</super>&middot CH₃I, as well as a study of the disolvated anion I<super>&minus</super>&middot: CH₃I)₂. The findings demonstrate the usefulness of this method as a probe of anion &ndash molecule solvation structure, long range electron &ndash molecule interactions, solvent electronic structure, and the influence of the cluster environment upon photodetachment dynamics. A detailed description of the experimental methods, including the construction and operation of the instrumentation, is presented. Applications of the method towards further study of electron &ndash neutral resonances and electron initiated chemical reactions are discussed.

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2011

Author dc:creator

• Van Duzor, Matthew

Contributors dc:contributor

• Richard Mabbs

• Physical Chemistry
• cluster anions
• photoelectron angular distributions
• photoelectron spectroscopy

Language dc:language

English (en)

DOI

https://doi.org/10.7936/K71R6NJF

OAI identifier oai:identifier

oai:openscholarship.wustl.edu:etd-1354