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Title: Gas-Phase Study of the Elementary Reaction of the D1-Ethynyl Radical (C2D; X2Σ+) with Propylene (C3H6; X1A') under Single-Collision Conditions

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Russian Academy of Sciences (RAS), Samara (Russian Federation); Samara National Research University (Russian Federation)
  3. Florida International Univ. (FIU), Miami, FL (United States)
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The bimolecular gas-phase reactions of the D1-ethynyl radical (C2D; X2Σ+) with propylene (C3H6; X1A’) and partially substituted D3-3,3,3-propylene (C2H3CD3; X1A’) were studied under single collision conditions utilizing the crossed molecular beams technique. Combining our laboratory data with electronic structure and statistical calculations, the D1-ethynyl radical is found to add without barrier to the C1 and C2 carbons of the propylene reactant, resulting in doublet C5H6D intermediate(s) with lifetime(s) longer than their rotational period(s). These intermediates undergo isomerization and unimolecular decomposition via atomic hydrogen loss through tight exit transition states forming predominantly cis/trans-3-penten-1-yne ((HCC)CH=CH(CH3)) and to a minor amount 3-methyl-3-buten-1-yne ((HCC)C(CH3)=CH2) via overall exoergic reactions. Although the title reaction does not lead to the cyclopentadiene molecule (c-C5H6, X1A1), high temperature environments can convert the identified acyclic C5H6 isomers through hydrogen atom assisted isomerization to cyclopentadiene (c-C5H6, X1A1). Since both the ethynyl radical and propylene reactants have been observed in cold interstellar environments such as TMC-1 and the reaction is exoergic and all barriers lie below the energy of the separated reactants, the these C5H6 product isomers are predicted to form in those low temperature regions.

Research Organization:
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1862627
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 126, Issue 11; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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