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Title: Infrared absorption of 3-propenonyl (⋅CH{sub 2}CHCO) radical generated upon photolysis of acryloyl chloride [CH{sub 2}CHC(O)Cl] in solid para-H{sub 2}

Irradiation at 193 nm of a p-H{sub 2} matrix containing acryloyl chloride CH{sub 2}CHC(O)Cl at 3.2 K yielded infrared absorption lines at 3143.6 (ν{sub 1}), 3057.0 (ν{sub 2}), 3048.0 (ν{sub 3}), 2103.1 (ν{sub 4}), 1461.0 (ν{sub 5}), 1349.8 (ν{sub 6}), 1223.7 (ν{sub 11}+ν{sub 12} or 2ν{sub 12}), 1092.8 (ν{sub 8}), 918.1 (ν{sub 9}), 691.0 (ν{sub 10}), 624.3 (ν{sub 11}), and 597.1 (ν{sub 12}) cm{sup −1} that are assigned to the 3-propenonyl (⋅CH{sub 2}CHCO) radical. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers and infrared intensities with those predicted with the B3PW91/aug-cc-pVDZ method. The observation is consistent with a major radical formation channel CH{sub 2}CHCO + Cl followed by escape of the Cl atom from the original p-H{sub 2} cage. The observation of 3-propenonyl (⋅CH{sub 2}CHCO) radical but not 3-propenalyl (s-cis- or s-trans-CH{sub 2}CHĊO) radical indicates that the former is the most stable isomer and that the barrier heights for conversion from s-cis- or s-trans-CH{sub 2}CHĊO to ⋅CH{sub 2}CHCO are small.
Authors:
 [1] ;  [1] ;  [2]
  1. Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China)
  2. (China)
Publication Date:
OSTI Identifier:
22220462
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 8; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; ABSORPTION; ALLOCATIONS; CHLORIDES; DENSITY FUNCTIONAL METHOD; DISSOCIATION; INFRARED SPECTRA; IRRADIATION; ISOMERIZATION; ORGANIC COMPOUNDS; PHOTOLYSIS; PHOTON-MOLECULE COLLISIONS; RADICALS; SOLIDS; VIBRATIONAL STATES