A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl
Abstract
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.
- Publication Date:
- Research Org.:
- Florida International Univ. (FIU), Miami, FL (United States); Univ. of Hawaii, Honolulu, HI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Russian Ministry of Science and Higher Education
- OSTI Identifier:
- 1619596
- Alternate Identifier(s):
- OSTI ID: 1594725; OSTI ID: 1603230
- Grant/Contract Number:
- FG02-04ER15570; FG02-03ER15411; 14.Y26.31.0020
- Resource Type:
- Published Article
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Name: Scientific Reports Journal Volume: 9 Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United Kingdom
- 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 Kingdom: 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 Kingdom. https://doi.org/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 Kingdom. https://doi.org/10.1038/s41598-019-53987-5.
@article{osti_1619596,
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 Kingdom},
year = {Tue Nov 26 00:00:00 EST 2019},
month = {Tue Nov 26 00:00:00 EST 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s41598-019-53987-5
https://doi.org/10.1038/s41598-019-53987-5
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 4 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Reaction of the ethynyl radical, C2H, with methylacetylene, CH3CCH, under single collision conditions: Implications for astrochemistry
journal, February 2001
- Stahl, Frank; von Ragué Schleyer, Paul; Bettinger, H. F.
- The Journal of Chemical Physics, Vol. 114, Issue 8
Interstellar Chemistry: A Strategy for Detecting Polycyclic Aromatic Hydrocarbons in Space
journal, March 2005
- Lovas, F. J.; McMahon, Robert J.; Grabow, Jens-Uwe
- Journal of the American Chemical Society, Vol. 127, Issue 12
Photodissociation dynamics of propyne at 157 nm
journal, April 2000
- Harich, S.; Lin, J. J.; Lee, Y. T.
- The Journal of Chemical Physics, Vol. 112, Issue 15
Untangling the chemical evolution of Titan's atmosphere and surface–from homogeneous to heterogeneous chemistry
journal, January 2010
- Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney
- Faraday Discussions, Vol. 147
A VUV Photoionization Study of the Formation of the Indene Molecule and Its Isomers
journal, June 2011
- Zhang, Fangtong; Kaiser, Ralf I.; Kislov, Vadim V.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 14
Crossed-Molecular-Beam Study on the Formation of Phenylacetylene from Phenyl Radicals and Acetylene
journal, September 2007
- Gu, Xibin; Zhang, Fangtong; Guo, Ying
- Angewandte Chemie International Edition, Vol. 46, Issue 36
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
H and D release in ∼243.1 nm photolysis of vibrationally excited 3ν1, 4ν1, and 4νCD overtones of propyne-d3
journal, May 2004
- Ganot, Yuval; Rosenwaks, Salman; Bar, Ilana
- The Journal of Chemical Physics, Vol. 120, Issue 18
A crossed beam and ab initio study of the C2(X1Σg+ /a3∏u)+C2H2(X1Σg+) reactions
journal, November 2003
- Kaiser, Ralf I.; Balucani, Nadia; Charkin, Dmitry O.
- Chemical Physics Letters, Vol. 382, Issue 1-2
Formation of Three C 4 H 3 N Isomers from the Reaction of CN (X 2 Σ + ) with Allene, H 2 CCCH 2 (X 1 A 1 ), and Methylacetylene, CH 3 CCH (X 1 A 1 ): A Combined Crossed Beam and Ab Initio Study
journal, May 2002
- Balucani, N.; Asvany, O.; Kaiser, R. -I.
- The Journal of Physical Chemistry A, Vol. 106, Issue 17
Selective Formation of Indene through the Reaction of Benzyl Radicals with Acetylene
journal, April 2015
- Parker, Dorian S. N.; Kaiser, Ralf. I.; Kostko, Oleg
- ChemPhysChem, Vol. 16, Issue 10
Gas-Phase Synthesis of Phenyl Oxoborane (C 6 H 5 BO) via the Reaction of Boron Monoxide with Benzene
journal, November 2013
- Parker, Dorian S. N.; Dangi, Beni B.; Balucani, Nadia
- The Journal of Organic Chemistry, Vol. 78, Issue 23
Reaction Dynamics of Phenyl Radicals (C 6 H 5 , X 2 A‘) with Methylacetylene (CH 3 CCH(X 1 A 1 )), Allene (H 2 CCCH 2 (X 1 A 1 )), and Their D4-Isotopomers
journal, November 2007
- Gu, Xibin; Zhang, Fangtong; Guo, Ying
- The Journal of Physical Chemistry A, Vol. 111, Issue 45
Exploring the Gas Phase Synthesis of the Elusive Class of Boronyls and the Mechanism of Boronyl Radical Reactions under Single Collision Conditions
journal, December 2016
- Kaiser, Ralf I.; Balucani, Nadia
- Accounts of Chemical Research, Vol. 50, Issue 5
A Combined Crossed Molecular Beam and ab Initio Study of the Reactions C 2 (X 1 ∑ g + , a 3 Π u ) + C 2 H 4 → n -C 4 H 3 (X 2 A‘) + H( 2 S 1/2 )
journal, November 2001
- Balucani, Nadia; Mebel, Alexander M.; Lee, Yuan T.
- The Journal of Physical Chemistry A, Vol. 105, Issue 43
Elucidating the Chemical Dynamics of the Elementary Reactions of the 1-Propynyl Radical (CH 3 CC; X 2 A 1 ) with Methylacetylene (H 3 CCCH; X 1 A 1 ) and Allene (H 2 CCCH 2 ; X 1 A 1 )
journal, June 2019
- He, Chao; Zhao, Long; Thomas, Aaron M.
- The Journal of Physical Chemistry A, Vol. 123, Issue 26
Chemical complexity in the Horsehead photodissociation region
journal, January 2014
- Guzmán, Viviana V.; Pety, Jérôme; Gratier, Pierre
- Faraday Discuss., Vol. 168
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
Experimental Investigation on the Formation of Carbon-Bearing Molecules in the Interstellar Medium via Neutral−Neutral Reactions
journal, May 2002
- Kaiser, Ralf I.
- Chemical Reviews, Vol. 102, Issue 5
Exchange reactions of alkali atoms with alkali halides: a collision complex mechanism
journal, January 1967
- Miller, W. B.; Safron, S. A.; Herschbach, D. R.
- Discussions of the Faraday Society, Vol. 44
Gas Phase Formation of the Interstellar Molecule Methyltriacetylene
journal, June 2019
- He, Chao; Thomas, Aaron M.; Galimova, Galiya R.
- ChemPhysChem, Vol. 20, Issue 15
Experimental and kinetic modeling study of premixed n-butylbenzene flames
journal, January 2017
- Yuan, Wenhao; Li, Yuyang; Wang, Zhandong
- Proceedings of the Combustion Institute, Vol. 36, Issue 1
Reaction dynamics of carbon-bearing radicals in circumstellar envelopes of carbon stars
journal, January 2006
- Gu, Xibin; Guo, Ying; Zhang, Fangtong
- Faraday Discussions, Vol. 133
Investigating repetitive reaction pathways for the formation of polycyclic aromatic hydrocarbons in combustion processes
journal, June 2017
- Hansen, Nils; Schenk, Marina; Moshammer, Kai
- Combustion and Flame, Vol. 180
Ab Initio G3-type/Statistical Theory Study of the Formation of Indene in Combustion Flames. I. Pathways Involving Benzene and Phenyl Radical †
journal, May 2007
- Kislov, V. V.; Mebel, A. M.
- The Journal of Physical Chemistry A, Vol. 111, Issue 19
Detection of the aromatic molecule benzonitrile ( c -C 6 H 5 CN) in the interstellar medium
journal, January 2018
- McGuire, Brett A.; Burkhardt, Andrew M.; Kalenskii, Sergei
- Science, Vol. 359, Issue 6372
Angular distributions of reactive scattering arising from persistent complexes with asymmetric top transition states
journal, August 1991
- Smith, D. J.; Grice, R.
- Molecular Physics, Vol. 73, Issue 6
Vibrational relaxation in jet‐cooled phenylalkynes
journal, June 1981
- Powers, D. E.; Hopkins, J. B.; Smalley, R. E.
- The Journal of Chemical Physics, Vol. 74, Issue 11
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
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
A Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH 3 CC)–Acetylene (HCCH) System and the Formation of Methyldiacetylene (CH 3 CCCCH)
journal, July 2018
- Thomas, Aaron M.; Zhao, Long; He, Chao
- The Journal of Physical Chemistry A, Vol. 122, Issue 33
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
The increasing chemical complexity of the Taurus dark clouds - Detection of CH3CCH and C4H
journal, August 1981
- Irvine, W. M.; Hoglund, B.; Friberg, P.
- The Astrophysical Journal, Vol. 248
Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH 3 CC)–1,3-Butadiene (CH 2 CHCHCH 2 ) System and the Formation of Toluene under Single Collision Conditions
journal, April 2019
- Thomas, Aaron M.; He, Chao; Zhao, Long
- The Journal of Physical Chemistry A, Vol. 123, Issue 19
Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames
journal, January 2018
- Ruwe, Lena; Moshammer, Kai; Hansen, Nils
- Physical Chemistry Chemical Physics, Vol. 20, Issue 16
Formation of benzene in the interstellar medium
journal, December 2010
- Jones, B. M.; Zhang, F.; Kaiser, R. I.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 2
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
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Crossed beam reaction of phenyl radicals with unsaturated hydrocarbon molecules. I. Chemical dynamics of phenylmethylacetylene (C6H5CCCH3;X 1A′) formation from reaction of C6H5(X 2A1) with methylacetylene, CH3CCH(X 1A1)
journal, March 2000
- Kaiser, R. I.; Asvany, O.; Lee, Y. T.
- The Journal of Chemical Physics, Vol. 112, Issue 11
Reaction Dynamics of Phenyl Radicals in Extreme Environments: A Crossed Molecular Beam Study
journal, February 2009
- Gu, Xibin; Kaiser, Ralf I.
- Accounts of Chemical Research, Vol. 42, Issue 2
Crossed Molecular Beam Study on the Formation of Phenylacetylene and Its Relevance to Titan’s Atmosphere
journal, April 2010
- Jones, Brant; Zhang, Fangtong; Maksyutenko, Pavlo
- The Journal of Physical Chemistry A, Vol. 114, Issue 16
A new Reference Chemical Composition for Tmc-1
journal, August 2016
- Gratier, P.; Majumdar, L.; Ohishi, M.
- The Astrophysical Journal Supplement Series, Vol. 225, Issue 2
Crossed-beam reaction of carbon atoms with hydrocarbon molecules. V. Chemical dynamics of n-C4H3 formation from reaction of C(3Pj) with allene, H2CCCH2(X 1A1)
journal, June 1999
- Kaiser, R. I.; Mebel, A. M.; Chang, A. H. H.
- The Journal of Chemical Physics, Vol. 110, Issue 21
Elementary reactions of the phenyl radical, C$_\mathsf{6}$H$_\mathsf{5}$, with C$_\mathsf{3}$H$_\mathsf{4}$ isomers, and of benzene, C$_\mathsf{6}$H$_\mathsf{6}$, with atomic carbon in extraterrestrial environments
journal, August 2003
- Kaiser, R. I.; Vereecken, L.; Peeters, J.
- Astronomy & Astrophysics, Vol. 406, Issue 2
Crossed beam investigation of elementary reactions relevant to the formation of polycyclic aromatic hydrocarbon (PAH)-like molecules in extraterrestrial environments
journal, April 2000
- Kaiser, R. I.; Asvany, O.; Lee, Y. T.
- Planetary and Space Science, Vol. 48, Issue 5
Neutral‐Neutral Reactions in the Interstellar Medium. I. Formation of Carbon Hydride Radicals via Reaction of Carbon Atoms with Unsaturated Hydrocarbons
journal, March 1997
- Kaiser, R. I.; Stranges, D.; Lee, Y. T.
- The Astrophysical Journal, Vol. 477, Issue 2
Crossed beam reaction of the cyano radical, CN(X 2Σ+), with methylacetylene, CH3CCH (X 1A1): Observation of cyanopropyne, CH3CCCN (X 1A1), and cyanoallene, H2CCCHCN (X 1A′)
journal, August 1999
- Huang, L. C. L.; Balucani, N.; Lee, Y. T.
- The Journal of Chemical Physics, Vol. 111, Issue 7
Formation of Curvature Subunit of Carbon in Combustion
journal, July 2016
- Wu, Xin-Zhou; Yao, Yang-Rong; Chen, Miao-Miao
- Journal of the American Chemical Society, Vol. 138, Issue 30
Global investigation of potential energy surfaces for the pyrolysis of C 1 –C 3 hydrocarbons: toward the development of detailed kinetic models from first principles
journal, January 2015
- Ryazantsev, Mikhail N.; Jamal, Adeel; Maeda, Satoshi
- Physical Chemistry Chemical Physics, Vol. 17, Issue 41
Reaction of Phenyl Radicals with Propyne
journal, February 2002
- Vereecken, Luc; Peeters, Jozef; Bettinger, Holger F.
- Journal of the American Chemical Society, Vol. 124, Issue 11
Crossed beam reaction of cyano radicals with hydrocarbon molecules. I. Chemical dynamics of cyanobenzene (C6H5CN; X 1A1) and perdeutero cyanobenzene (C6D5CN; X 1A1) formation from reaction of CN(X 2Σ+) with benzene C6H6(X 1A1g), and d6-benzene C6D6(X 1A1g)
journal, October 1999
- Balucani, N.; Asvany, O.; Chang, A. H. H.
- The Journal of Chemical Physics, Vol. 111, Issue 16
Indene Formation under Single-Collision Conditions from the Reaction of Phenyl Radicals with Allene and Methylacetylene-A Crossed Molecular Beam and Ab Initio Study
journal, September 2011
- Parker, Dr Dorian S. N.; Zhang, Dr Fangtong; Kaiser, Dr Ralf I.
- Chemistry - An Asian Journal, Vol. 6, Issue 11
Hydrogen Abstraction/Acetylene Addition Revealed
journal, June 2014
- Parker, Dorian S. N.; Kaiser, Ralf I.; Troy, Tyler P.
- Angewandte Chemie International Edition, Vol. 53, Issue 30
Gaussian-3 theory using coupled cluster energies
journal, November 1999
- Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.
- Chemical Physics Letters, Vol. 314, Issue 1-2
The Formation of Nitriles in Hydrocarbon-Rich Atmospheres of Planets and Their Satellites: Laboratory Investigations by the Crossed Molecular Beam Technique
journal, September 2001
- Kaiser, Ralf I.; Balucani, Nadia
- Accounts of Chemical Research, Vol. 34, Issue 9
A Crossed Beam and ab Initio Investigation of the Reaction of Hydrogen Sulfide, H 2 S(X 1 A 1 ), with Dicarbon Molecules, C 2 (X 1 Σ g + )
journal, May 2002
- Kaiser, R. I.; Yamada, M.; Osamura, Y.
- The Journal of Physical Chemistry A, Vol. 106, Issue 19
Aromatic ring formation in opposed-flow diffusive 1,3-butadiene flames
journal, January 2017
- Moshammer, Kai; Seidel, Lars; Wang, Yu
- Proceedings of the Combustion Institute, Vol. 36, Issue 1
Discrimination of product isomers in the photodissociation of propyne and allene at 193 nm
journal, March 1999
- Sun, Weizhong; Yokoyama, Keiichi; Robinson, Jason C.
- The Journal of Chemical Physics, Vol. 110, Issue 9
Crossed beams reaction of atomic carbon, C(3Pj), with d6-benzene, C6D6(X 1A1g): Observation of the per-deutero-1,2-didehydro- cycloheptatrienyl radical, C7D5(X 2B2)
journal, April 1999
- Kaiser, R. I.; Hahndorf, I.; Huang, L. C. L.
- The Journal of Chemical Physics, Vol. 110, Issue 13
Chemical dynamics of cyclopropynylidyne (c-C[sub 3]H; X[sup 2]B[sub 2]) formation from the reaction of C([sup 1]D) with acetylene, C[sub 2]H[sub 2](X [sup 1]Σ[sub g][sup +])
journal, January 2001
- Kaiser, R. I.; Mebel, A. M.; Lee, Y. T.
- The Journal of Chemical Physics, Vol. 114, Issue 1
Long-range transition state theory
journal, May 2005
- Georgievskii, Yuri; Klippenstein, Stephen J.
- The Journal of Chemical Physics, Vol. 122, Issue 19
Chemical dynamics of d1-methyldiacetylene (CH3CCCCD; X 1A1) and d1-ethynylallene (H2CCCH(C2D); X 1A′) formation from reaction of C2D(X 2Σ+) with methylacetylene, CH3CCH(X 1A1)
journal, February 2001
- Kaiser, R. I.; Chiong, C. C.; Asvany, O.
- The Journal of Chemical Physics, Vol. 114, Issue 8
Kinetics of the Thermal Reaction of H Atoms with Propyne
journal, May 2010
- Rosado-Reyes, Claudette M.; Manion, Jeffrey A.; Tsang, Wing
- The Journal of Physical Chemistry A, Vol. 114, Issue 18
Dynamics of persistent collision complexes in molecular beam reactive scattering
journal, September 1995
- Grice, Roger
- International Reviews in Physical Chemistry, Vol. 14, Issue 2