ORCID

https://orcid.org/0000-0003-2849-9379

Date of Award

9-7-2023

Author's School

Graduate School of Arts and Sciences

Author's Department

Chemistry

Degree Name

Doctor of Philosophy (PhD)

Degree Type

Dissertation

Abstract

Comparing experimental photoelectron angular distributions to theoretical predictions for direct detachment is a valuable tool for indicating more complex detachment pathways, such as those which access temporary anion states. This is exemplified by resonance mediated detachment from NiO2−. The presence of forbidden transitions and deviations in photoelectron angular distribution and relative transition intensities indicate a resonance, which is further supported with multireference calculations. In detachment processes that produce a neutral molecule with a permanent dipole, the quality of angular distribution predictions suffer by treating the outgoing electron as a free particle. To improve upon this issue, angular distribution prediction methods are developed to incorporate the effect of the charge-dipole interaction. To achieve this, the photoelectron continuum is expressed in terms of point dipole wavefunctions. The results of this model are then compared to experimental results from CN− and SO− photodetachment. In both cases, predicted angular distributions are closer to experimental values when incorporating a point dipole potential. Although the point dipole approach improves upon standard prediction techniques, it is still an approximation and can be further improved by using a physical dipole model in the future, allowing for adjustable charge separation between the two poles.

Language

English (en)

Chair and Committee

Richard Mabbs

Available for download on Thursday, August 28, 2025

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