Date of Award

Spring 1995

Degree Type

Thesis - Restricted

Degree Name

Master of Science (MS)

Department

Chemistry

Abstract

Norrish type II elimination of formate esters was studied by laser photolysis of the gas phase ester samples coupled with time-resolved infrared diode laser absorption spectroscopy of the formic acid photo fragment. The role of molecular structure of formate esters on the quantum yield was characterized. The photodissociation dynamics of isobutyl formate was investigated with the view of determining the nascent rotational energy distribution of the formic acid photoproduct. Semi empirical calculations were performed to provide information about energies and geometries of reactants, products, diradicals and transition states and information about reaction pathways. It was fpund that the Norrish type II elimination quantum yield for a primary, secondary and tertiary y-H atom is about 1:3:9. The initial experimental results from photolysis of isobutyl formate indicate that the nascent rotational energy distribution of the formic acid photofragment is nonstatistical and more formic acid molecules rotate about the carbonyl group than rotate in the molecular plane when they are eliminated. Transition states of the y-H abstraction for six formate esters were located using AMl. The singlet and triplet diradicals of ethyl formate were found using the same method.

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