Hypervalent Radical Chemistry and Photochemistry

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With funding from the Organic Dynamics Program Professor Turacek of the University of Washington will study by the use of a tandem mass spectrometer the behavior of hypervalent radicals. Organic heteroatom molecules containing oxygen, nitrogen, phosphorus, and sulfur will be used to generate hypervalent radicals formed by femtosecond electron transfer in the gas phase. Four aspects of the hypervalent radicals will be studied. They are: (1) photochemistry; (2) probing protonation sites by radical dissociations; (3) intramolecular electron transfer; and (4) hydrogen atom transfer. Novel carbon containing molecules that may also contain sulfur, nitrogen, phosphorus, or oxygen will be subjected to high energy electromagnetic radiation to prepare species with very short lifetimes and unusual electron arrangements. The behavior of these species in the gas phase will be measured by a mass spectrometer of unique design. Theoretical computations will be used to simulate the data acquired from the experiments. These results will help define what variables must be modified for computational experiments using high performance computers.