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Title: Dynamics of carbon-hydrogen and carbon-methyl exchanges in the collision of {sup 3}P atomic carbon with propene

We investigated the dynamics of the reaction of {sup 3}P atomic carbon with propene (C{sub 3}H{sub 6}) at reactant collision energy 3.8 kcal mol{sup −1} in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. Products C{sub 4}H{sub 5}, C{sub 4}H{sub 4}, C{sub 3}H{sub 3}, and CH{sub 3} were observed and attributed to exit channels C{sub 4}H{sub 5} + H, C{sub 4}H{sub 4} + 2H, and C{sub 3}H{sub 3} + CH{sub 3}; their translational-energy distributions and angular distributions were derived from the measurements of product time-of-flight spectra. Following the addition of a {sup 3}P carbon atom to the C=C bond of propene, cyclic complex c-H{sub 2}C(C)CHCH{sub 3} undergoes two separate stereoisomerization mechanisms to form intermediates E- and Z-H{sub 2}CCCHCH{sub 3}. Both the isomers of H{sub 2}CCCHCH{sub 3} in turns decompose to C{sub 4}H{sub 5} + H and C{sub 3}H{sub 3} + CH{sub 3}. A portion of C{sub 4}H{sub 5} that has enough internal energy further decomposes to C{sub 4}H{sub 4} + H. The three exit channels C{sub 4}H{sub 5} + H, C{sub 4}H{sub 4} + 2H, and C{sub 3}H{sub 3} + CH{sub 3} have average translational energy releases 13.5, 3.2, and 15.2 kcal mol{sup −1}, respectively, corresponding to fractions 0.26, 0.41, and 0.26more » of available energy deposited to the translational degrees of freedom. The H-loss and 2H-loss channels have nearly isotropic angular distributions with a slight preference at the forward direction particularly for the 2H-loss channel. In contrast, the CH{sub 3}-loss channel has a forward and backward peaked angular distribution with an enhancement at the forward direction. Comparisons with reactions of {sup 3}P carbon atoms with ethene, vinyl fluoride, and vinyl chloride are stated.« less
Authors:
; ; ;  [1]
  1. National Synchrotron Radiation Research Center (NSRRC), 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China)
Publication Date:
OSTI Identifier:
22251523
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 17; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANGULAR DISTRIBUTION; CARBON; COLLISIONS; DEGREES OF FREEDOM; DEPOSITS; ENERGY SPECTRA; ETHYLENE; FLUORIDES; HYDROGEN; IONIZATION; PROPARGYL RADICALS; PROPYLENE; SYNCHROTRONS; VINYL CHLORIDE