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Elucidating the Chemical Dynamics of the Elementary Reactions of the 1-Propynyl Radical (CH3CC; X2A1) with Methylacetylene (H3CCCH; X1A1) and Allene (H2CCCH2; X1A1)

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [2];  [3];  [3];  [2]
  1. Univ. of Hawai'i at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
  2. Univ. of Hawai'i at Manoa, Honolulu, HI (United States)
  3. Florida International Univ., Miami, FL (United States)
+ Show Author Affiliations
The reactions of the 1-propynyl radical (CH3CC; X2A1) with two C3H4 isomers, methylacetylene (H3CCCH; X1A1) and allene (H2CCCH2; X1A1), along with their (partially) deuterated counterparts were explored at collision energies of 37 kJ mol–1, exploiting crossed molecular beams to unravel the chemical reaction dynamics to synthesize distinct C6H6 isomers under single collision conditions. The forward convolution fitting of the laboratory data along with ab initio and statistical calculations revealed that both reactions have no entrance barrier, proceed via indirect (complex-forming) reaction dynamics involving C6H7 intermediates with life times longer than their rotation period(s), and are initiated by the addition of the 1-propynyl radical with its radical center to the π-electron density of the unsaturated hydrocarbon at the terminal carbon atoms of methylacetylene (C1) and allene (C1/C3). In the methylacetylene system, the initial collision complexes undergo unimolecular decomposition via tight exit transition states by atomic hydrogen loss, forming dimethyldiacetylene (CH3CCCCCH3) and 1-propynylallene (H3CCCHCCCH2) in overall exoergic reactions (123 and 98 kJ mol–1) with a branching ratio of 9.4 ± 0.1; the methyl group of the 1-propynyl reactant acts solely as a spectator. On the other hand, in the allene system, our experimental data exhibit the formation of the fulvene (c-C5H4CH2) isomer via a six-step reaction sequence with two higher energy isomers—hexa-1,2-dien-4-yne (H2CCCHCCCH3) and hexa-1,4-diyne (HCCCH2CCCH3)—also predicted to be formed based on our statistical calculations. Here, the pathway to fulvene advocates that, in the allene–1-propynyl system, the methyl group of the 1-propynyl reactant is actively engaged in the reaction mechanism to form fulvene. Because both reactions are barrierless and exoergic and all transition states are located below the energy of the separated reactants, the hydrogen-deficient C6H6 isomers identified in our investigation are predicted to be synthesized in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and their moons such as Titan along with cold molecular clouds such as Taurus Molecular Cloud-1.
Research Organization:
Florida International Univ., Miami, FL (United States); Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1603180
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 26 Vol. 123; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl journal November 2019
Directed Gas‐Phase Synthesis of Triafulvene under Single‐Collision Conditions journal September 2019
Directed Gas‐Phase Synthesis of Triafulvene under Single‐Collision Conditions journal October 2019
A combined experimental and computational study on the reaction dynamics of the 1-propynyl radical (CH 3 CC; X 2 A 1 ) with ethylene (H 2 CCH 2 ; X 1 A 1g ) and the formation of 1-penten-3-yne (CH 2 CHCCCH 3 ; X 1 A′) journal January 2019

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