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Title: Theoretical Study of the Reaction of the Methylidyne Radical (CH; X2Π) with 1-Butyne (CH3CH2CCH; X1A')

Abstract

In this study, ab initio CCSD(T)-F12/cc-pVTZ-f12//ωB97X-D/6-311G(d,p) + ZPE(ωB97X-D/6-311G(d,p)) calculations were carried out to unravel the area of the C5H7 potential energy surface accessed by the reaction of the methylidyne radical with 1-butyne. The results were utilized in Rice-Ramsperger-Kassel-Marcus calculations of the product branching ratios at the zero pressure limit. The preferable reaction mechanism has been shown to involve (nearly) instantaneous decomposition of the initial reaction adducts, whose structures are controlled by the isomeric form of the C4H6 reactant. If CH adds to the triple CΞC bond in the entrance reaction channel, the reaction is predicted to predominantly form the methylenecyclopropene + methyl (CH3) and cyclopropenylidene + ethyl (C2H5) products roughly in a 2:1 ratio. CH insertion into a C-H bond in the methyl group of 1-butyne is anticipated to preferentially form ethylene + propargyl (C3H3) by the C-C bond β-scission in the initial complex, whereas CH insertion into C-H of the CH2 group would predominantly produce vinylacetylene + methyl (CH3) also by the C-C bond β-scission in the adduct. The barrierless and highly exoergic CH + 1-butyne reaction, facile in cold molecular clouds, is not likely to lead to the carbon skeleton molecular growth but generates C4H4 isomers methylenecyclopropene, vinylacetylene,more » and 1,2,3-butatriene and smaller C2 and C3 hydrocarbons such as methyl, ethyl, and propargyl radicals, ethylene, and cyclopropenylidene.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Russian Academy of Sciences (RAS), Samara (Russian Federation). P.N. Lebedev Physical Institute; Samara National Research Univ. (Russian Federation)
  2. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  3. Florida International Univ. (FIU), Miami, FL (United States)
Publication Date:
Research Org.:
Florida International Univ. (FIU), Miami, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Higher Education and Science of the Russian Federation
OSTI Identifier:
1843965
Grant/Contract Number:  
FG02-04ER15570; FG02-03ER15411; 075-15-2021-597
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 125; Journal Issue: 43; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nikolayev, Anatoliy A., Azyazov, Valeriy N., Kaiser, Ralf I., and Mebel, Alexander M. Theoretical Study of the Reaction of the Methylidyne Radical (CH; X2Π) with 1-Butyne (CH3CH2CCH; X1A'). United States: N. p., 2021. Web. doi:10.1021/acs.jpca.1c07519.
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Nikolayev, Anatoliy A., Azyazov, Valeriy N., Kaiser, Ralf I., & Mebel, Alexander M. Theoretical Study of the Reaction of the Methylidyne Radical (CH; X2Π) with 1-Butyne (CH3CH2CCH; X1A'). United States. https://doi.org/10.1021/acs.jpca.1c07519
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Nikolayev, Anatoliy A., Azyazov, Valeriy N., Kaiser, Ralf I., and Mebel, Alexander M. Thu . "Theoretical Study of the Reaction of the Methylidyne Radical (CH; X2Π) with 1-Butyne (CH3CH2CCH; X1A')". United States. https://doi.org/10.1021/acs.jpca.1c07519. https://www.osti.gov/servlets/purl/1843965.
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@article{osti_1843965,
title = {Theoretical Study of the Reaction of the Methylidyne Radical (CH; X2Π) with 1-Butyne (CH3CH2CCH; X1A')},
author = {Nikolayev, Anatoliy A. and Azyazov, Valeriy N. and Kaiser, Ralf I. and Mebel, Alexander M.},
abstractNote = {In this study, ab initio CCSD(T)-F12/cc-pVTZ-f12//ωB97X-D/6-311G(d,p) + ZPE(ωB97X-D/6-311G(d,p)) calculations were carried out to unravel the area of the C5H7 potential energy surface accessed by the reaction of the methylidyne radical with 1-butyne. The results were utilized in Rice-Ramsperger-Kassel-Marcus calculations of the product branching ratios at the zero pressure limit. The preferable reaction mechanism has been shown to involve (nearly) instantaneous decomposition of the initial reaction adducts, whose structures are controlled by the isomeric form of the C4H6 reactant. If CH adds to the triple CΞC bond in the entrance reaction channel, the reaction is predicted to predominantly form the methylenecyclopropene + methyl (CH3) and cyclopropenylidene + ethyl (C2H5) products roughly in a 2:1 ratio. CH insertion into a C-H bond in the methyl group of 1-butyne is anticipated to preferentially form ethylene + propargyl (C3H3) by the C-C bond β-scission in the initial complex, whereas CH insertion into C-H of the CH2 group would predominantly produce vinylacetylene + methyl (CH3) also by the C-C bond β-scission in the adduct. The barrierless and highly exoergic CH + 1-butyne reaction, facile in cold molecular clouds, is not likely to lead to the carbon skeleton molecular growth but generates C4H4 isomers methylenecyclopropene, vinylacetylene, and 1,2,3-butatriene and smaller C2 and C3 hydrocarbons such as methyl, ethyl, and propargyl radicals, ethylene, and cyclopropenylidene.},
doi = {10.1021/acs.jpca.1c07519},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 43,
volume = 125,
place = {United States},
year = {Thu Oct 21 00:00:00 EDT 2021},
month = {Thu Oct 21 00:00:00 EDT 2021}
}
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Works referenced in this record:

Identification of C 5 H x Isomers in Fuel-Rich Flames by Photoionization Mass Spectrometry and Electronic Structure Calculations
journal, April 2006

  • Hansen, Nils; Klippenstein, Stephen J.; Miller, James A.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 13
  • DOI: 10.1021/jp0569685

Photoionization mass spectrometric studies and modeling of fuel-rich allene and propyne flames
journal, January 2007

  • Hansen, Nils; Miller, James A.; Taatjes, Craig A.
  • Proceedings of the Combustion Institute, Vol. 31, Issue 1
  • DOI: 10.1016/j.proci.2006.07.045

Identification of isomeric C5H3 and C5H5 free radicals in flame with tunable synchrotron photoionization
journal, June 2006

Detection of C5 in the Circumstellar Shell of IRC+10216
journal, May 1989

A combined crossed beam and ab initio investigation on the reaction of carbon species with C4H6 isomers. I. The 1,3-butadiene molecule, H2CCHCHCH2(X1A′)
journal, December 2000

  • Hahndorf, I.; Lee, H. Y.; Mebel, A. M.
  • The Journal of Chemical Physics, Vol. 113, Issue 21
  • DOI: 10.1063/1.1290285

A combined crossed beam and ab initio investigation on the reaction of carbon species with C4H6 isomers. II. The dimethylacetylene molecule, H3CCCCH3(X1A1g)
journal, December 2000

  • Huang, L. C. L.; Lee, H. Y.; Mebel, A. M.
  • The Journal of Chemical Physics, Vol. 113, Issue 21
  • DOI: 10.1063/1.1290286

Formation of the 2,4-Pentadiynyl-1 Radical (H 2 CCCCCH, X 2 B 1 ) in the Crossed Beams Reaction of Dicarbon Molecules with Methylacetylene
journal, May 2006

  • Guo, Ying; Gu, Xibin; Balucani, Nadia
  • The Journal of Physical Chemistry A, Vol. 110, Issue 19
  • DOI: 10.1021/jp058280y

Unimolecular Decomposition of Chemically Activated Pentatetraene (H 2 CCCCCH 2 ) Intermediates:  A Crossed Beams Study of Dicarbon Molecule Reactions with Allene
journal, September 2006

  • Guo, Ying; Gu, Xibin; Zhang, Fangtong
  • The Journal of Physical Chemistry A, Vol. 110, Issue 37
  • DOI: 10.1021/jp062447l

Potential Energy Surface and Product Branching Ratios for the Reaction of Dicarbon, C 2 (X 1 Σ g + ), with Methylacetylene, CH 3 CCH(X 1 A 1 ):  An Ab Initio/RRKM Study
journal, February 2006

  • Mebel, A. M.; Kislov, V. V.; Kaiser, R. I.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 7
  • DOI: 10.1021/jp054309m

Unimolecular decomposition of chemically activated singlet and triplet D3-methyldiacetylene molecules
journal, August 2007

On the Formation of Resonantly Stabilized C 5 H 3 Radicals—A Crossed Beam and Ab Initio Study of the Reaction of Ground State Carbon Atoms with Vinylacetylene
journal, February 2011

  • Parker, Dorian S. N.; Zhang, Fangtong; Kim, Y. Seol
  • The Journal of Physical Chemistry A, Vol. 115, Issue 5
  • DOI: 10.1021/jp109800h

Theoretical and kinetic study of reaction C2H + C3H6 on the C5H7 potential energy surface
journal, November 2014

  • Gong, Chun-Ming; Ning, Hong-Bo; Li, Ze-Rong
  • Theoretical Chemistry Accounts, Vol. 134, Issue 1
  • DOI: 10.1007/s00214-014-1599-x

Mystery of 1-Vinylpropargyl Formation from Acetylene Addition to the Propargyl Radical: An Open-and-Shut Case
journal, March 2017

An Aromatic Universe–A Physical Chemistry Perspective
journal, April 2021

A crossed molecular beam study on the synthesis of the interstellar 2,4-pentadiynylidyne radical (HCCCCC)
journal, October 2008

  • Zhang, Fangtong; Kim, Yong Seol; Zhou, Li
  • The Journal of Chemical Physics, Vol. 129, Issue 13
  • DOI: 10.1063/1.2987366

Gas-Phase Formation of C 5 H 6 Isomers via the Crossed Molecular Beam Reaction of the Methylidyne Radical (CH; X 2 Π) with 1,2-Butadiene (CH 3 CHCCH 2 ; X 1 A′)
journal, January 2021

  • He, Chao; Nikolayev, Anatoliy A.; Zhao, Long
  • The Journal of Physical Chemistry A, Vol. 125, Issue 1
  • DOI: 10.1021/acs.jpca.0c08731

Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
  • DOI: 10.1039/b810189b

A simple and efficient CCSD(T)-F12 approximation
journal, December 2007

  • Adler, Thomas B.; Knizia, Gerald; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 127, Issue 22
  • DOI: 10.1063/1.2817618

Simplified CCSD(T)-F12 methods: Theory and benchmarks
journal, February 2009

  • Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 130, Issue 5
  • DOI: 10.1063/1.3054300

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Prediction of Reaction Barriers and Thermochemical Properties with Explicitly Correlated Coupled-Cluster Methods: A Basis Set Assessment
journal, August 2012

  • Zhang, Jinmei; Valeev, Edward F.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 9
  • DOI: 10.1021/ct3005547

Henry Eyring, S. H. Lin, S. M. Lin: Basic Chemical Kinetics. John Wiley & Sons, New York, Chichester, Brisbane, Toronto 1980. 493 Seiten, Preis: £ 20. -
journal, July 1981

  • Hofacker, G. L.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 85, Issue 7
  • DOI: 10.1002/bbpc.19810850721

Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study
journal, April 2004

  • Kislov, V. V.; Nguyen, T. L.; Mebel, A. M.
  • The Journal of Chemical Physics, Vol. 120, Issue 15
  • DOI: 10.1063/1.1676275

Reaction Mechanism and Product Branching Ratios of the CH + C 3 H 8 Reaction: A Theoretical Study
journal, June 2014

  • Ribeiro, Joao Marcelo; Mebel, Alexander M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 39
  • DOI: 10.1021/jp502128z

Reaction Mechanism and Product Branching Ratios of the CH + C 3 H 6 Reaction: A Theoretical Study
journal, March 2016

  • Ribeiro, Joao Marcelo; Mebel, Alexander M.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 11
  • DOI: 10.1021/acs.jpca.5b12588
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