| This research has focused on the kinetics of the OH-initiated oxidation of several oxygenated compounds including 2-methyl-3-buten-2-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, and hydroxyacetone, as the chemistry of these compounds in the atmosphere begins with the their reaction with the OH radical. Measurements of the rate constants for the reactions of these compounds with the OH radical were made as a function of temperature and pressure using a discharge-flow system coupled with resonance fluorescence or laser-induced fluorescence detection of OH. These studies have revealed that the mechanism for the reaction of oxygenated volatile organic compounds with OH are complex, displaying non-traditonal pressure and temperature dependencies. To gain insight into the chemical mechanism for these reactions, the structure and energetics of some important intermediates along the potential energy surface for these reactions were examined using ab-initio molecular orbital methods. The theoretical results were used in conjunction with the experimental measurements to improve our understanding of the factors controlling the reactivity of these compounds. |
