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Title: Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium

Abstract

Bimolecular reactions of phenyl-type radicals with the C4 and C5 hydrocarbons vinylacetylene and (methyl-substituted) 1,3-butadiene have been found to synthesize polycyclic aromatic hydrocarbons (PAHs) with naphthalene and 1,4-dihydronaphthalene cores in exoergic and entrance barrierless reactions under single-collision conditions. The reaction mechanism involves the initial formation of a van der Waals complex and addition of a phenyl-type radical to the C1 position of a vinyl-type group through a submerged barrier. Investigations suggest that in the hydrocarbon reactant, the vinyl-type group must be in conjugation with a –C≡CH or –HC=CH2 group to form a resonantly stabilized free radical intermediate, which eventually isomerizes to a cyclic intermediate followed by hydrogen loss and aromatization (PAH formation). Finally, the vinylacetylene-mediated formation of PAHs might be expanded to more complex PAHs, such as anthracene and phenanthrene, in cold molecular clouds via barrierless reactions involving phenyl-type radicals, such as naphthyl, which cannot be accounted for by the classical hydrogen abstraction–acetylene addition mechanism.

Authors:
 [1];  [1];  [2]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1602874
Grant/Contract Number:  
FG02-03ER15411; FG02-04ER15570
Resource Type:
Accepted Manuscript
Journal Name:
Annual Review of Physical Chemistry
Additional Journal Information:
Journal Volume: 66; Journal Issue: 1; Journal ID: ISSN 0066-426X
Publisher:
Annual Reviews
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cold molecular clouds; neutral-neutral reactions; nonequilibrium chemistry; aromaticity; resonantly stabilized free radical; ISM

Citation Formats

Kaiser, Ralf I., Parker, Dorian S. N., and Mebel, Alexander M. Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium. United States: N. p., 2014. Web. doi:10.1146/annurev-physchem-040214-121502.
Kaiser, Ralf I., Parker, Dorian S. N., & Mebel, Alexander M. Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium. United States. https://doi.org/10.1146/annurev-physchem-040214-121502
Kaiser, Ralf I., Parker, Dorian S. N., and Mebel, Alexander M. Thu . "Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium". United States. https://doi.org/10.1146/annurev-physchem-040214-121502. https://www.osti.gov/servlets/purl/1602874.
@article{osti_1602874,
title = {Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium},
author = {Kaiser, Ralf I. and Parker, Dorian S. N. and Mebel, Alexander M.},
abstractNote = {Bimolecular reactions of phenyl-type radicals with the C4 and C5 hydrocarbons vinylacetylene and (methyl-substituted) 1,3-butadiene have been found to synthesize polycyclic aromatic hydrocarbons (PAHs) with naphthalene and 1,4-dihydronaphthalene cores in exoergic and entrance barrierless reactions under single-collision conditions. The reaction mechanism involves the initial formation of a van der Waals complex and addition of a phenyl-type radical to the C1 position of a vinyl-type group through a submerged barrier. Investigations suggest that in the hydrocarbon reactant, the vinyl-type group must be in conjugation with a –C≡CH or –HC=CH2 group to form a resonantly stabilized free radical intermediate, which eventually isomerizes to a cyclic intermediate followed by hydrogen loss and aromatization (PAH formation). Finally, the vinylacetylene-mediated formation of PAHs might be expanded to more complex PAHs, such as anthracene and phenanthrene, in cold molecular clouds via barrierless reactions involving phenyl-type radicals, such as naphthyl, which cannot be accounted for by the classical hydrogen abstraction–acetylene addition mechanism.},
doi = {10.1146/annurev-physchem-040214-121502},
journal = {Annual Review of Physical Chemistry},
number = 1,
volume = 66,
place = {United States},
year = {Thu Nov 20 00:00:00 EST 2014},
month = {Thu Nov 20 00:00:00 EST 2014}
}

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