Abstract

This dissertation aims to provide deeper insight into understanding the dynamics of the photodetached electrons and the nature of the parent species. The dissertation provides examples of quasi-bound states of the anion embedded in the continuum of states associated with the neutral species, and shows how they manifest in experimental data, deviating from expectations of direct detachment. This dissertation is primarily computational and applies and develops electronic-structure and continuum models, respectively, and a newly implemented physical dipole treatment of the photoelectron to account for these resonances and to interpret experimental photoelectron imaging data. The content of the dissertation is divided into three parts. The first part discusses how resonances in iodide methyl and ethyl halide clusters account for the differences observed in photoelectron angular distributions across halides (X = I, Br, Cl). Here, the complex absorbing potential method is applied to learn about the resonance states. These calculations identify σ-type shape resonances that account for the halide-dependent deviations of the PADs from direct-detachment expectations. The second part focuses on the development of a physical dipole model to treat the photoelectron continuum and subsequently uses it to calculate anisotropy parameters and relative cross-sections. The calculated values are then benchmarked against the available experimental results of AgF−, CN−, and CuO−. The physical-dipole model reproduces the experimental trends in β and relative cross sections substantially better than free-particle and point-dipole treatments. The third and final part discusses the changes in the relative cross-section for photodetachment of the highly polar anion, CuO−. The presence of a dipole-bound state is thoroughly investigated through experimental and theoretical data analyses, and the presence of a resonance in the continuum is probed using a stabilization method. The analysis rules out vibrational autodetachment from a DBS as the origin of the near-threshold cross-section maxima, and instead supports an electronically unbound resonance lying just above the neutral ground state.

Committee Chair

Richard Mabbs

Committee Members

Anthony Schlimgen; Courtney Reichhardt; Richard Loomis; Robert Wexler

Degree

Doctor of Philosophy (PhD)

Author's Department

Chemistry

Author's School

Graduate School of Arts and Sciences

Document Type

Dissertation

Date of Award

8-11-2026

Language

English (en)

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