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Title: A Barrierless Pathway Accessing the C 9H 9 and C 9H 8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl

Abstract

The crossed molecular beams reactions of the 1-propynyl radical (CH 3CC ; X 2A 1) with benzene (C 6H 6; X1A1g) and D6-benzene (C 6D 6; X 1A 1g) were conducted to explore the formation of C 9H 8 isomers under single-collision conditions. The underlying reaction mechanisms were unravelled through the combination of the experimental data with electronic structure and statistical RRKM calculations. These data suggest the formation of 1-phenyl-1-propyne (C 6H 5CCCH 3) via the barrierless addition of 1-propynyl to benzene forming a low-lying doublet C 9H 9 intermediate that dissociates by hydrogen atom emission via a tight transition state. In accordance with our experiments, RRKM calculations predict that the thermodynamically most stable isomer – the polycyclic aromatic hydrocarbon (PAH) indene – is not formed via this reaction. With all barriers lying below the energy of the reactants, this reaction is viable in the cold interstellar medium where several methyl-substituted molecules have been detected. Its underlying mechanism therefore advances our understanding of how methyl-substituted hydrocarbons can be formed under extreme conditions such as those found in the molecular cloud TMC-1. Implications for the chemistry of the 1-propynyl radical in astrophysical environments are also discussed.

Authors:
 [1];  [1]; ORCiD logo [1];  [2];  [2]
  1. Univ. of Hawaii, Honolulu, HI (United States)
  2. Samara National Research Univ. (Russia); Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Florida International Univ., Miami, FL (United States); Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Russian Ministry of Science and Higher Education
OSTI Identifier:
1594725
Grant/Contract Number:  
FG02-04ER15570; FG02-03ER15411; 14.Y26.31.0020
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Thomas, Aaron M., Doddipatla, Srinivas, Kaiser, Ralf I., Galimova, Galiya R., and Mebel, Alexander M. A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl. United States: N. p., 2019. Web. doi:10.1038/s41598-019-53987-5.
Thomas, Aaron M., Doddipatla, Srinivas, Kaiser, Ralf I., Galimova, Galiya R., & Mebel, Alexander M. A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl. United States. doi:10.1038/s41598-019-53987-5.
Thomas, Aaron M., Doddipatla, Srinivas, Kaiser, Ralf I., Galimova, Galiya R., and Mebel, Alexander M. Tue . "A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl". United States. doi:10.1038/s41598-019-53987-5. https://www.osti.gov/servlets/purl/1594725.
@article{osti_1594725,
title = {A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl},
author = {Thomas, Aaron M. and Doddipatla, Srinivas and Kaiser, Ralf I. and Galimova, Galiya R. and Mebel, Alexander M.},
abstractNote = {The crossed molecular beams reactions of the 1-propynyl radical (CH3CC ; X2A1) with benzene (C6H6; X1A1g) and D6-benzene (C6D6; X1A1g) were conducted to explore the formation of C9H8 isomers under single-collision conditions. The underlying reaction mechanisms were unravelled through the combination of the experimental data with electronic structure and statistical RRKM calculations. These data suggest the formation of 1-phenyl-1-propyne (C6H5CCCH3) via the barrierless addition of 1-propynyl to benzene forming a low-lying doublet C9H9 intermediate that dissociates by hydrogen atom emission via a tight transition state. In accordance with our experiments, RRKM calculations predict that the thermodynamically most stable isomer – the polycyclic aromatic hydrocarbon (PAH) indene – is not formed via this reaction. With all barriers lying below the energy of the reactants, this reaction is viable in the cold interstellar medium where several methyl-substituted molecules have been detected. Its underlying mechanism therefore advances our understanding of how methyl-substituted hydrocarbons can be formed under extreme conditions such as those found in the molecular cloud TMC-1. Implications for the chemistry of the 1-propynyl radical in astrophysical environments are also discussed.},
doi = {10.1038/s41598-019-53987-5},
journal = {Scientific Reports},
number = 1,
volume = 9,
place = {United States},
year = {2019},
month = {11}
}

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