Unimolecular Dissociation of the Methylsulfonyl Radical and its CH3OSO Isomer Laurie J. Butler, Department of Chemistry, The University of Chicago, Chicago,

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Unimolecular Dissociation of the Methylsulfonyl Radical and its CH3OSO Isomer Laurie J. Butler, Department of Chemistry, The University of Chicago, Chicago, IL 60637 Sulfur-containing radicals in the troposphere play a dynamic role in the oxidation of dimethyl sulfide (DMS) to sulfur dioxide. This work investigates the unimolecular dissociation of CH3SO2, a key radical intermediate in the DMS oxidation mechanism originally proposed by A. R. Ravishankara. We use state-of-the-art molecular beam scattering and imaging techniques to generate the radical under collision free conditions and probe its dissociation to CH3 + SO2. Our experimentally-measured dissociation barrier of 14 +/- 2 kcal/mol benchmarks the high level ab initio electronic structure calculations by K.- C. Lau.