Electronic Theses and Dissertations

Date of Award

1-1-2023

Document Type

Dissertation

Degree Name

Ph.D. in Chemistry

First Advisor

Ryan C. Fortenberry

Second Advisor

Nathan Hammer

Third Advisor

Steven Davis

School

University of Mississippi

Relational Format

dissertation/thesis

Abstract

Modelling of spectroscopic properties is useful for detection of species which are di_- cult to study in the laboratory. Full reproduction of electronic spectra depends upon reliable spectroscopic data of electronically excited states. However, no means of producing accurate fundamental vibrational frequencies of these states exist. This doctoral work consists of applications of theoretical spectra for prediction and identification of novel species as well as attempts to extend this methodology to effectively treat electronically excited states. The former includes the study of conformers of methanediol and a set of [Al,N,C,O] isomers. The latter is done using equation-of-motion theory to form quartic force fields based on a Taylor series approximation of the internuclear potential portion of the vibrational Hamiltonian. Several novel approaches are explored, including an approximation which treats reference state energies and excitation energies separately and approaches based on equation-of-motion ionization potential.

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