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Title: Photofragment energy distributions and dissociation pathways in dimethyl sulfoxide

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.479000· OSTI ID:341363
; ; ;  [1]
  1. Department of Chemistry, University of Wisconsin---Madison, Madison, Wisconsin 53706 (United States)

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{sub 3} and CH{sub 3}SO as primary fragments and CH{sub 3} and SO as secondary fragments. From CH{sub 3} quantum yield measurements, we find that secondary decomposition is minor for 222 nm photolysis, occurring in only about 10{percent} of the fragments, but it increases to about 30{percent} in the 210 nm photolysis. Laser-induced fluorescence measurements on the B{sup 3}{Sigma}{sup {minus}}{l_arrow}X{sup 3}{Sigma}{sup {minus}} transition of SO in the 235 to 280 nm region determine the internal energy of that photoproduct. We compare our results to a simple statistical model that captures the essential features of the decomposition, predicting both the extent of secondary decomposition and the recoil energy of the primary and secondary methyl fragments. {copyright} {ital 1999 American Institute of Physics.}

OSTI ID:
341363
Journal Information:
Journal of Chemical Physics, Vol. 110, Issue 22; Other Information: PBD: Jun 1999
Country of Publication:
United States
Language:
English