ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The reaction of ground state carbon atoms, C(3Pj), with dimethylacetylene, H3CCCCH3, was studied at three collision energies between 21.2 and 36.9 kJmol−1 employing the crossed molecular beam approach. Our experiments were combined with ab initio and RRKM calculations. It is found that the reaction is barrierless via a loose, early transition state located at the centrifugal barrier following indirect scattering dynamics through a complex. C(3Pj) attacks the π system of the dimethylacetylene molecule to form a dimethylcyclopropenylidene intermediate either in one step via an addition to C1 and C2 of the acetylenic bond or through an addition to only one carbon atom to give a short-lived cis/trans dimethylpropenediylidene intermediates followed by ring closure. The cyclic intermediate ring opens to a linear dimethylpropargylene radical which rotates almost parallel to the total angular momentum vector J. This complex fragments to atomic hydrogen and a linear 1-methylbutatrienyl radical, H2CCCCCH3(X2A″), via a tight exit transition state located about 18 kJmol−1 above the separated products. The experimentally determined exothermicity of 190±25 kJmol−1 is in strong agreement with our calculated data of 180±10 kJmol−1. The explicit verification of the carbon versus hydrogen exchange pathway together with the first identification of the H2CCCCCH3 radical represents a third pathway to form chain C5H5 radicals in the reactions of C(3Pj) with C4H6 isomers under single collision conditions. Previous experiments of atomic carbon with the 1,3-butadiene isomer verified the formation of 1- and 3-vinylpropargyl radicals, HCCCHC2H3(X2A″), and H2CCCC2H3(X2A″), respectively. In high-density environments such as combustion flames and circumstellar envelopes of carbon stars, these linear isomers can undergo collision-induced ring closure(s) and/or H atom migration(s) which can lead to the cyclopentadienyl radical. The latter is thought to be a crucial reactive intermediate in soot formation and possibly in the production of polycyclic aromatic hydrocarbon molecules in outflow of carbon stars. Likewise, a H atom catalyzed isomerization can interconvert the 3-vinylpropargyl and the 1-methylbutatrienyl radical. © 2000 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1290286
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