Molecular Beam and Imaging Studies of Radical Reaction Pathways and Chemical Product Branching

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In this project, funded by the Experimental Physical Chemistry Program of the Chemistry Division, Professor Laurie J. Butler of the University of Chicago will study the unimolecular decay of selected radical species as a function of energy of the radical. Molecular beam and imaging techniques will be used to perform two sets of experiments. 1) The first set will probe competing unimolecular dissociation channels of isomerically-selected hydrocarbon radicals as function of internal energy in the dissociating radical isomer on the ground state potential surface. Two key C4H7 radical isomers will be investigated. 2) The second part of the research deals with the dynamics of the carbene biradical intermediates of the oxygen-triplet-P + alkyne reactions. In the oxygen + acetylene system, the dynamics is claimed to proceed via intersystem crossing from the triplet to singlet ketene. This work will probe the importance of intersystem crossing in this class of bimolecular reactions and thereby provide data to test theoretical models for this reaction. The work will also address larger alkyne + oxygen reactions. The experiments of the first part will be carried out at the Advanced Light Source of the Lawrence Berkeley National Laboratory, while those of the second part will be done in the laboratory of the PI's home institution. This research will be done with student participants. The students will acquire knowledge and skills in one of the forefront areas of contemporary physical chemistry. They will thereby be prepared for advanced studies or employment in academia, industry, or national laboratories.