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PAH Formation under Single Collision Conditions - Reaction of Phenyl Radical and 1,3-Butadiene to form 1,4-Dihydronaphthalene.
MedLine Citation:
PMID:  22497458     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The crossed beam reactions of the phenyl radical (C6H5, X2A1) with 1,3-butadiene (C4H6, X1Ag) and D6-1,3-butadiene (C4D6, X1Ag) as well as of the D5-phenyl radical (C6D5, X2A1) with 2,3-D2-1,3-buta¬diene and 1,1,4,4-D4-1,3-butadiene were carried out under single collision condi¬ti¬ons at collision energies of about 55 kJmol-1. Experimentally, the bicyclic 1,4-dihydro¬naphthalene molecule was identified as a major product of this reaction (58 ± 15 %) with the 1-phenyl-1,3-butadiene contributing 34 ± 10 % The reaction is initiated by a barrier-less addition of the phenyl radical to the terminal carbon atom of the 1,3-butadiene (C1/C4) to form a bound intermediate; the latter underwent hydrogen elimination from the terminal CH2 group of the 1,3-butadiene molecule leading to 1-phenyl-trans-1,3-butadiene through a submerged barrier. The dominant product - 1,4-dihydro¬naphthalene - is formed via an isomerization of the adduct by ring closure and emission of the hydrogen atom from the phenyl moiety at the bridging carbon atom through a tight exit transitions state located about 31 kJmol-1 above the separated products. The hydrogen atom was found to leave the decomposing complex almost parallel to the total angular momentum vector and perpendicularly to the rotation plane of the decomposing intermediate. The de-facto barrier-less formation of the 1,4-dihydronaphthalene molecule involving a single collision between a phenyl radicals and 1,3-butadiene represents an important step in the formation of polycyclic aromatic hydrocarbons (PAHs) and their partially hydrogenated counterparts in combustion and interstellar chemistry.
Authors:
Ralf I Kaiser; Dorian Sebastian Neville Parker; Fangtong Zhang; Alexander Landera; Vadim V Kislov; Alexander Moiseevich Mebel
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-4-12
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  -     ISSN:  1520-5215     ISO Abbreviation:  -     Publication Date:  2012 Apr 
Date Detail:
Created Date:  2012-4-13     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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