Thesis (Ph. D.)--Florida State University, 2005. / Advisor: Dr. Nicholas E. Bonesteel, Florida State University, College of Arts and Sciences, Dept. of Physics. Title and description from dissertation home page (viewed Sept. 16, 2005). Document formatted into pages; contains x, 136 pages. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1966. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D. D.)--University of Wisconsin--Madison, 1982. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin, 1967. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The binding energies and momentum distributions of all of the valence orbitals of (CH₃)₂O, PH₃, CH₄ and SiH₄ have been measured by high momentum resolution electron momentum spectroscopy. The binding energy spectra have been compared to Green's function and configuration interaction calculations from the literature and with new calculations performed in collaboration with co-workers at Indiana University and Universitat Braunschweig. For PH₃, CH₄ and SiH₄, near Hartree-Fock limit calculations of the momentum distributions and very accurate calculations of the ion-neutral overlap using MRSD-CI wavefunctions to describe the ion and target have been performed in collaboration with co-workers at Indiana University. Good agreement is obtained between the (CH₃)₂O measurements and the momentum distributions calculated from relatively simple wavefunctions, except in the case of the outermost orbital. The effects of diffuse and polarization functions in the basis sets, and also the influence of molecular geometry, have been investigated. Comparison of the momentum distributions of the outermost orbitals of H₂O, CH₃OH and (CH₃)₂O demonstrates a delocalization of charge density with methyl substitution. The measured momentum distributions of PH₃, CH₄ and SiH₄ are compared with near Hartree-Fock limit calculations as well as ion-neutral overlap calculations in which the ion and neutral wavefunctions are described by multireference, singly and doubly excited, configuration interaction calculations. In each case, the experimental results are well modelled by the near Hartree-Fock limit calculations, and there is little difference between the Hartree-Fock limit and ion-neutral overlap calculations. A significant splitting of the 4a₁ (inner valence) pole strength is observed for PH₃, but the inner valence strength is largely contained in the main peak for both CH₄ and SiH₄. Green's function calculations quantitatively reproduce these results. Ion-neutral overlap calculations using MRSD-CI wavefunctions to describe the ion and target have been performed for HF, HCl, Ne and Ar. These are compared with previously published EMS measurements of the momentum distributions. Very poor agreement between theory and experiment is obtained for HF and HCl. The theoretical and experimental results for all of the hydrides CH₄-HF and SiH₄-HCl as well as Ne and Ar are reviewed. / Science, Faculty of / Chemistry, Department of / Graduate

Recently there has been considerable interest in studying the interactions of orbitals which were formerly thought of as localized and isolated. The technique of Photoelectron Spectroscopy (PES) is well suited for this and PE spectra are presented here for the series of five membered ring molecules consisting of tetrahydrofuran, γ-butyrolactone, 2,5-dihydrofuran, γ-crotonolactone, 1,3-dioxolane, ethylene carbonate, vinylene carbonate, 4-cyclopentene 1,3-dione, maleimide and maleic anhydride. In these spectra the IP's of the carbonyl oxygen lone pairs and the higher π levels have been assigned and trends in these IP's established in the series. For the carbonyl oxygen lone pair, the shift in IP caused by various groups (oxygen atoms α to the carbonyl, double bonds in the ring and additional carbonyl groups β to the one in question) are found to be approximately additive, which suggests that inductive effects are important. However, the pattern of π IP's must be rationalized in terms of both inductive and resonance effects. Finally some correlations with UV spectra for the last three molecules are presented. / Science, Faculty of / Chemistry, Department of / Graduate

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