Date of Award
Spring 2013
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Reid, Scott A.
Second Advisor
Sem, Daniel
Third Advisor
Kincaid, James
Abstract
ABSTRACT
"MOLECULAR SPECTROSCOPY AND DYNAMICS OF REACTIVE CHEMICAL INTERMEDIATES STUDIED USING LASER INDUCED FLUORESCENCE (LIF), SINGLE VIBRONIC LEVEL (SVL) EMISSION AND RESONANCE ENHANCED MULTIPHOTON IONIZATION (REMPI) SPECTROMETRY"
Lloyd Muzangwa, B.Sc. (Hons, Biochemistry).
Marquette University, 2013
In the studies of complex chemical processes, it is necessary to postulate mechanisms involving transient intermediates such as radicals, ions, and pre-reactive complexes. The detection and characterization of these intermediates affords in ideal cases determination of the detailed chemical mechanism, which, in turn, can permit the development of rational strategies for removing undesired products and enhancing the yield of the desired species. This dissertation describes spectroscopic study of transient molecules and molecular complexes. Laser Induced Fluorescence (LIF), Single Vibronic Level (SVL) emission and Resonance Enhanced Multiple Photon Ionization (REMPI) spectroscopy has been used to probe the electronic states of NiI, NiBr, NiCl, CCN and chlorobenzene clusters (ClBz)n where n = 1-4. In this work, term energies and a complete set of vibrational parameters were derived for all the electronic states accessible for NiI, NiBr, NiCl and CCN. These vibrational parameters were compared to the recent high level ab initio calculations. REMPI spectra of chlorobenzene clusters formed in a He/Ar supersonic jet were obtained. Different types of non-covalent interactions (ð-ð stacking, CH/ð interactions, and halogen bonding) were found to be in operation in the ClBz clusters. To rationalize the experimental results, the clusters were characterized computationally using Density Functional Theory (DFT) and Time-Dependent DFT methods in combination with correlation consistent basis sets.