Dissociation photochemistry of alkyl radicals
Description
For most chemical reactions, two events are involved: the breaking of the old bond (or bonds) and the formation of the new bond (or bonds). In order to influence the outcome of a reaction, chemists have used many methods to achieve selective cleavage of the targeted bond. In this dissertation, studies on site-specific cleavage of alkyl radicals by excimer lasers are presented and possible practical applications are discussed. The propensity of C-H bond cleavage at the $\beta$ position for small organic radicals such as the ethyl and the n-propyl was observed in the experiment results. A two-color photolysis process was implemented to confirm that the dissociation route unequivocally involves photolysis of a radical intermediate. Markov chain methods have been used to simulate partially the scrambling of the radicals in an effort to gain more insights into the dissociation process. Site-specific research has also been conducted on systems that are relevant to semiconductor manufacturing. Extensions to bimolecular systems are also presented. Here, results of the reaction between chlorine atoms and selectively-deuterated propanes are provided