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A Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH 3 CC)–Acetylene (HCCH) System and the Formation of Methyldiacetylene (CH 3 CCCCH)

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [2];  [3];  [2]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
  2. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  3. Florida International Univ., Miami, FL (United States)
+ Show Author Affiliations
We investigated the 1-propynyl (CH3CC; X2A1) plus acetylene/acetylene-d2 (HCCH/DCCD; X1Σg+) under single-collision conditions using the crossed molecular beams method. The reaction was found to produce C5H4 plus atomic hydrogen (H) via an indirect reaction mechanism with a reaction energy of -123 ± 18 kJ mol–1. Using the DCCD isotopologue, we confirmed that the hydrogen atom is lost from the acetylene reactant. Our computational analysis suggests the reaction proceeds by the barrierless addition of the 1-propynyl radical to acetylene, resulting in C5H5 intermediate(s) that dissociate preferentially to methyldiacetylene (CH3CCCCH; X1A1) via hydrogen atom emission with a computed reaction energy of -123 ± 4 kJ mol–1. The barrierless nature of this reaction scheme suggests the 1-propynyl radical may be a key intermediate in hydrocarbon chain growth in cold molecular clouds like TMC-1, where methyl-substituted (poly)acetylenes are known to exist.
Research Organization:
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-03ER15411
OSTI ID:
1603088
Alternate ID(s):
OSTI ID: 1539179
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: 33 Vol. 122; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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