Reaction mechanism studies of unsaturated molecules using photofragment translational spectroscopy

A number of molecules have been studied using the technique of photofragment translational spectroscopy. In Chapter One a brief introduction to the experimental technique is given. The focus is on the type of information that can be obtained, which includes product identities, translational energy distributions, and angular distributions, and how this information can be used to predict reaction mechanisms. The relevance of these studies to bulk experiments is also addressed.;In Chapter Two the infrared multiphoton dissociation (IRMPD) of acetic acid is discussed. Carbon dioxide and methane were observed for the first time as products from dissociation under collisionless conditions. The product translational energy distribution peaks well away from zero, which supports a four-center transition state. A previously observed channel, resulting in the formation of water and ketene, was verified. With a laser fluence of 12 J/cm;Chapter Three relates an IRMPD experiment of hexafluoropropene. Two primary channels and one secondary channel were identified. The predominant channel produces CFCF;In Chapter Four the ultraviolet (UV) dissociation of hexafluoropropene is investigated. At 193 nm one primary channel results in the loss of a fluorine atom; from the maximum translational energy release, a value of 121 kcal/mol was found for the C-F bond dissociation energy. The two other channels are CF;Chapter Five explores the IRMPD of octafluoro-1-butene and octafluoro-2-butene. The predominant reaction in octafluoro-1-butene at moderate laser fluences is cleavage of a carbon-carbon single bond to give the products CF...