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Photolysis of dimethyl sulfoxide in a molecular beam with 210 and 222 nm photons reveals the decomposition mechanism and energy disposal in the products. Using vacuum ultraviolet light and a time-of-flight spectrometer, we identify CH 3 and CH 3 SO as primary fragments and CH 3 and SO as secondary fragments. From CH 3 quantum yield measurements, we find that secondary decomposition is minor for 222 nm photolysis, occurring in only about 10% of the fragments, but it increases to about 30% in thedoi:10.1063/1.479000 fatcat:hxn4fk5eenctxk5owce7oweqou