A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene – toward the formation of methylnaphthalenes
Abstract
Crossed molecular beam experiments and electronic structure calculations on the reaction of the meta-tolyl radical with vinylacetylene were conducted to probe the formation of methyl-substituted naphthalene isomers. We present the compelling evidence that under single collision conditions 1- and 2-methylnaphthalene can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the meta-tolyl radical and vinylacetylene. The electronic structure calculations, conducted at the UCCSD(T)-F12b/cc-pVDZ//UM06-2x/cc-pVTZ + ZPE(UM06-2x/cc-pVTZ) level of theory, reveal that this reaction is initiated by the barrierless addition of the meta-tolyl radical to the terminal vinyl carbon (C1) of vinylacetylene, via a van-der-Waals complex implying that this mechanism can play a key role in forming methyl-substituted PAHs in low temperature extreme environments such as the low temperature interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer solar system. The reaction mechanism, proposed from the C11H11 potential energy surface, involves a sequence of isomerizations involving hydrogen transfer and ring closure, followed by hydrogen dissociation, which eventually leads to 1- and 2-methylnaphthalene in an overall exoergic process.
- Authors:
-
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Kyoto Univ. (Japan). Fukui Inst. for Fundamental Chemistry
- Kyoto Univ. (Japan). Fukui Inst. for Fundamental Chemistry; Emory Univ., Atlanta, GA (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); US Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1602913
- Grant/Contract Number:
- FG02-03ER15411; FA9550-10-1-0304; FA9550-12-1-0472
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 33; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Yang, Tao, Muzangwa, Lloyd, Kaiser, Ralf I., Jamal, Adeel, and Morokuma, Keiji. A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene – toward the formation of methylnaphthalenes. United States: N. p., 2015.
Web. doi:10.1039/c5cp03285g.
Yang, Tao, Muzangwa, Lloyd, Kaiser, Ralf I., Jamal, Adeel, & Morokuma, Keiji. A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene – toward the formation of methylnaphthalenes. United States. https://doi.org/10.1039/c5cp03285g
Yang, Tao, Muzangwa, Lloyd, Kaiser, Ralf I., Jamal, Adeel, and Morokuma, Keiji. Fri .
"A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene – toward the formation of methylnaphthalenes". United States. https://doi.org/10.1039/c5cp03285g. https://www.osti.gov/servlets/purl/1602913.
@article{osti_1602913,
title = {A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene – toward the formation of methylnaphthalenes},
author = {Yang, Tao and Muzangwa, Lloyd and Kaiser, Ralf I. and Jamal, Adeel and Morokuma, Keiji},
abstractNote = {Crossed molecular beam experiments and electronic structure calculations on the reaction of the meta-tolyl radical with vinylacetylene were conducted to probe the formation of methyl-substituted naphthalene isomers. We present the compelling evidence that under single collision conditions 1- and 2-methylnaphthalene can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the meta-tolyl radical and vinylacetylene. The electronic structure calculations, conducted at the UCCSD(T)-F12b/cc-pVDZ//UM06-2x/cc-pVTZ + ZPE(UM06-2x/cc-pVTZ) level of theory, reveal that this reaction is initiated by the barrierless addition of the meta-tolyl radical to the terminal vinyl carbon (C1) of vinylacetylene, via a van-der-Waals complex implying that this mechanism can play a key role in forming methyl-substituted PAHs in low temperature extreme environments such as the low temperature interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer solar system. The reaction mechanism, proposed from the C11H11 potential energy surface, involves a sequence of isomerizations involving hydrogen transfer and ring closure, followed by hydrogen dissociation, which eventually leads to 1- and 2-methylnaphthalene in an overall exoergic process.},
doi = {10.1039/c5cp03285g},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 33,
volume = 17,
place = {United States},
year = {Fri Jul 17 00:00:00 EDT 2015},
month = {Fri Jul 17 00:00:00 EDT 2015}
}
Web of Science
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