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• W3110692007 abstract "The reaction between ground-state carbon atoms, C(3Pj), and methylacetylene, CH3CCH (X1A1), was studied at average collision energies of 20.4 and 33.2 kJ mol−1 using the crossed molecular beams technique. Product angular distributions and time-of-flight spectra of C4H3 at m/e=51 were recorded. Forward-convolution fitting of the data yields weakly polarized center-of-mass angular flux distributions isotropic at lower, but forward scattered with respect to the carbon beam at a higher collision energy. The translational energy flux distributions peak at 30–60 kJ mol−1 and show an average fractional translational energy release of 22%–30%. The maximum energy release as well as the angular distributions are consistent with the formation of the n-C4H3 radical in its electronic ground state. Reaction dynamics inferred from these distributions indicate that the carbon atom attacks the π-orbitals of the methylacetylene molecule via a loose, reactant like transition state located at the centrifugal barrier. The initially formed triplet 1-methylpropendiylidene complex rotates in a plane almost perpendicular to the total angular momentum vector around the BC-axes and undergoes [2,3]-hydrogen migration to triplet 1-methylpropargylene. Within 1–2 ps, the complex decomposes via C–H bond cleavage to n-C4H3 and atomic hydrogen. The exit transition state is found to be tight and located at least 30–60 kJ mol−1 above the products. The explicit identification of the n-C4H3 radical under single collision conditions represents a further example of a carbon–hydrogen exchange in reactions of ground state carbon atoms with unsaturated hydrocarbons. This channel opens a versatile pathway to synthesize extremely reactive hydrocarbon radicals relevant to combustion processes as well as interstellar chemistry." @default.
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• W3110692007 date "1996-11-15" @default.
• W3110692007 modified "2023-09-23" @default.
• W3110692007 title "Crossed-beam reaction of carbon atoms with hydrocarbon molecules. II. Chemical dynamics of <i>n</i>-C4H3 formation from reaction of C(3<i>P</i> <i>j</i>) with methylacetylene, CH3CCH (<i>X</i>1<i>A</i>1)" @default.
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• W3110692007 doi "https://doi.org/10.1063/1.472677" @default.
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