This work seeks a deeper understanding of the mechanisms of chemical reactions by computing classical trajectories (the detailed sequence of atomic motions that occurs as starting materials are transformed into products) using a combination of quantum mechanics and classical mechanics. Dr. Doubleday will examine several reaction types: reactions of oxygen atoms with radicals (unstable odd-electron molecules); reactions of negatively charged ions with molecules containing the carbonyl group, including ester hydrolysis; studies of specific vibrational energy requirements in cycloadditions; reactions involving carbenes (unstable molecules with a divalent carbon atom); and hydrocarbon rearrangements that involve short-lived biradical intermediates. Atomic oxygen reactions are important in the upper atmosphere, polymer incineration, and combustion generally. Carbonyl reactions with negative ions are common in organic and biological chemistry. The three other projects have wide relevance to organic reactivity, and seek to improve our understanding of the flow of energy from reactants to products. An important component of this project is the training of undergraduate students in scientific research. Students typically join Dr. Doubleday's research group in the summer after completing Organic Chemistry in the spring, are paid a summer research stipend, then continue research in the academic year and present their work the following spring at the National Meeting of the American Chemical Society. Since research is collaborative and students learn from each other, the work fosters group skills as well as individual achievement. As part of his dissemination effort, Dr. Doubleday's trajectory program is available and is currently being used in research groups at other academic institutions. Benefits to society at large will emerge from a deeper understanding of the mechanisms of chemical reactions sought in Dr. Doubleday's research. Since kinetic models of combustion, atmospheric, and environmental chemistry can ultimately affect governmental policy on air and water quality and climate change, the broadest impact of this project will be progress in chemical understanding that contributes to improvements in environmental quality and human health generally.
