Exploring the Chemical Dynamics of Phenylethynyl Radical (C 6 H 5 CC; X 2 A 1 ) Reactions with Allene (H 2 CCCH 2 ; X 1 A 1 ) and Methylacetylene (CH 3 CCH; X 1 A 1 )

Goettl, Shane J.; Yang, Zhenghai; Kollotzek, Siegfried; Paul, Dababrata; Kaiser, Ralf I.; Somani, Ankit; Portela-Gonzalez, Adrian; Sander, Wolfram; Nikolayev, Anatoliy A.; Azyazov, Valeriy N.; Mebel, Alexander M.

doi:10.1021/acs.jpca.3c03077

Title: Exploring the Chemical Dynamics of Phenylethynyl Radical (C ₆ H ₅ CC; X ² A ₁ ) Reactions with Allene (H ₂ CCCH ₂ ; X ¹ A ₁ ) and Methylacetylene (CH ₃ CCH; X ¹ A ₁ )

Journal Article · Tue Jul 04 00:00:00 EDT 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.3c03077· OSTI ID:1988095

Goettl, Shane J. ^[1]; Yang, Zhenghai ^[1]; Kollotzek, Siegfried ^[1]; Paul, Dababrata ^[1];

^[1]; Somani, Ankit ^[2];

^[2];

^[2]; Nikolayev, Anatoliy A. ^[3]; Azyazov, Valeriy N. ^[4];

^[5]

Department of Chemistry, University of Hawaii at Ma̅noa, Honolulu, Hawaii 96822, United States
Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, Bochum 44801, Germany
Samara National Research University, Samara 443086, Russia
Lebedev Physical Institute, Samara 443011, Russia
Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States

The bimolecular gas-phase reactions of the phenylethynyl radical (C₆H₅CC, X²A₁) with allene (H₂CCCH₂), allene-d₄ (D₂CCCD₂), and methylacetylene (CH₃CCH) were studied under single-collision conditions utilizing the crossed molecular beams technique and merged with electronic structure and statistical calculations. The phenylethynyl radical was found to add without an entrance barrier to the C₁ carbon of the allene and methylacetylene reactants, resulting in doublet C₁₁H₉ collision complexes with lifetimes longer than their rotational periods. These intermediates underwent unimolecular decomposition via atomic hydrogen loss through tight exit transition states in facile radical addition hydrogen atom elimination mechanisms forming predominantly 3,4- pentadien-1-yn-1-ylbenzene (C₆H₅CCCHCCH₂) and 1-phenyl-1,3-pentadiyne (C₆H₅CCCCCH₃) in overall exoergic reactions (–110 kJ mol^–1 and –130 kJ mol^–1) for the phenylethynyl–allene and phenylethynyl–methylacetylene systems, respectively. These barrierless reaction mechanisms mirror those of the ethynyl radical (C₂H, X²Σ⁺) with allene and methylacetylene forming predominantly ethynylallene (HCCCHCCH₂) and methyldiacetylene (HCCCCCH₃), respectively, suggesting that in the aforementioned reactions the phenyl group acts as a spectator. These molecular mass growth processes are accessible in lowtemperature environments such as cold molecular clouds (TMC-1) or Saturn’s moon Titan, efficiently incorporating a benzene ring into unsaturated hydrocarbons.

View Journal Article

Cite

Export

Save

Research Organization:: University of Hawai'i at Manoa, Honolulu, HI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Austrian Science Fund (FWF)

Grant/Contract Number:: FG02-03ER15411; W1259-N27

OSTI ID:: 1988095

Alternate ID(s):: OSTI ID: 1989445; OSTI ID: 1989590

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Vol. 127 Journal Issue: 27; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Reaction of the ethynyl radical, C2H, with methylacetylene, CH3CCH, under single collision conditions: Implications for astrochemistry Stahl, Frank; von Ragué Schleyer, Paul; Bettinger, H. F. The Journal of Chemical Physics, Vol. 114, Issue 8 https://doi.org/10.1063/1.1331360	journal	February 2001
Effects of C1-C3 hydrocarbon blending on aromatics formation in 1-butene counterflow flames Baroncelli, Martina; Mao, Qian; Pitsch, Heinz Combustion and Flame, Vol. 230 https://doi.org/10.1016/j.combustflame.2021.111427	journal	August 2021
Photodissociation dynamics of propyne at 157 nm Harich, S.; Lin, J. J.; Lee, Y. T. The Journal of Chemical Physics, Vol. 112, Issue 15 https://doi.org/10.1063/1.481316	journal	April 2000
Discovery of the propargyl radical (CH₂CCH) in TMC-1: One of the most abundant radicals ever found and a key species for cyclization to benzene in cold dark clouds Agúndez, M.; Cabezas, C.; Tercero, B. Astronomy & Astrophysics, Vol. 647 https://doi.org/10.1051/0004-6361/202140553	journal	March 2021
π and σ-Phenylethynyl Radicals and Their Isomers o-, m-, and p-Ethynylphenyl: Structures, Energetics, and Electron Affinities Sreeruttun, Raj K.; Ramasami, Ponnadurai; Wannere, Chaitanya S. The Journal of Physical Chemistry A, Vol. 112, Issue 13 https://doi.org/10.1021/jp0763329	journal	March 2008
Organic Molecules in the Interstellar Medium, Comets, and Meteorites: A Voyage from Dark Clouds to the Early Earth Ehrenfreund, Pascale; Charnley, Steven B. Annual Review of Astronomy and Astrophysics, Vol. 38, Issue 1 https://doi.org/10.1146/annurev.astro.38.1.427	journal	September 2000
H and D release in ∼243.1 nm photolysis of vibrationally excited 3ν1, 4ν1, and 4νCD overtones of propyne-d3 Ganot, Yuval; Rosenwaks, Salman; Bar, Ilana The Journal of Chemical Physics, Vol. 120, Issue 18 https://doi.org/10.1063/1.1698679	journal	May 2004
Molecular-growth pathways in premixed flames of benzene and toluene doped with propyne Hansen, N.; Yang, B.; Braun-Unkhoff, M. Combustion and Flame, Vol. 243 https://doi.org/10.1016/j.combustflame.2022.112075	journal	September 2022
Products of the Propargyl Self-Reaction at High Temperatures Investigated by IR/UV Ion Dip Spectroscopy Constantinidis, P.; Hirsch, F.; Fischer, I. The Journal of Physical Chemistry A, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpca.6b08750	journal	December 2016
Discovery of two new interstellar molecules with QUIJOTE: HCCCHCCC and HCCCCS Fuentetaja, R.; Agúndez, M.; Cabezas, C. Astronomy & Astrophysics, Vol. 667 https://doi.org/10.1051/0004-6361/202245018	journal	November 2022
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 ) He, Chao; Zhao, Long; Thomas, Aaron M. The Journal of Physical Chemistry A, Vol. 123, Issue 26 https://doi.org/10.1021/acs.jpca.9b03746	journal	June 2019
Experimental Investigation on the Formation of Carbon-Bearing Molecules in the Interstellar Medium via Neutral−Neutral Reactions Kaiser, Ralf I. Chemical Reviews, Vol. 102, Issue 5 https://doi.org/10.1021/cr970004v	journal	May 2002
Gas Phase Formation of the Interstellar Molecule Methyltriacetylene He, Chao; Thomas, Aaron M.; Galimova, Galiya R. ChemPhysChem, Vol. 20, Issue 15 https://doi.org/10.1002/cphc.201900305	journal	June 2019
Reaction dynamics of carbon-bearing radicals in circumstellar envelopes of carbon stars Gu, Xibin; Guo, Ying; Zhang, Fangtong Faraday Discussions, Vol. 133 https://doi.org/10.1039/b516457e	journal	January 2006
An experimental and kinetic modeling study of benzene pyrolysis with C2−C3 unsaturated hydrocarbons Hamadi, Alaa; Sun, Wenyu; Abid, Said Combustion and Flame, Vol. 237 https://doi.org/10.1016/j.combustflame.2021.111858	journal	March 2022
Electron Bombardment Molecular Beam Detector Brink, Gilbert O. Review of Scientific Instruments, Vol. 37, Issue 7 https://doi.org/10.1063/1.1720347	journal	July 1966
Mass spectrum of the butadiynyl radical (C4H; X2∑+) Gu, Xibin; Guo, Ying; Kaiser, Ralf I. International Journal of Mass Spectrometry, Vol. 246, Issue 1-3 https://doi.org/10.1016/j.ijms.2005.07.011	journal	November 2005
Homolytic aromatic substitution by phenylethynyl radicals Martelli, G.; Spagnolo, P.; Tiecco, M. Journal of the Chemical Society B: Physical Organic https://doi.org/10.1039/j29700001413	journal	January 1970
Phenylethynyl: matrix isolation electron spin resonance and molecular orbital study Kasai, Paul H.; McBay, Henry C. The Journal of Physical Chemistry, Vol. 88, Issue 24 https://doi.org/10.1021/j150668a037	journal	November 1984
Mystery of 1-Vinylpropargyl Formation from Acetylene Addition to the Propargyl Radical: An Open-and-Shut Case da Silva, Gabriel The Journal of Physical Chemistry A, Vol. 121, Issue 10 https://doi.org/10.1021/acs.jpca.6b12996	journal	March 2017
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008
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) Thomas, Aaron M.; Zhao, Long; He, Chao The Journal of Physical Chemistry A, Vol. 122, Issue 33 https://doi.org/10.1021/acs.jpca.8b05530	journal	July 2018
Kinetic modeling study of benzene and PAH formation in laminar methane flames Jin, Hanfeng; Frassoldati, Alessio; Wang, Yizun Combustion and Flame, Vol. 162, Issue 5 https://doi.org/10.1016/j.combustflame.2014.11.031	journal	May 2015
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 Thomas, Aaron M.; He, Chao; Zhao, Long The Journal of Physical Chemistry A, Vol. 123, Issue 19 https://doi.org/10.1021/acs.jpca.9b00092	journal	April 2019
Photoinduced Mechanism of Formation and Growth of Polycyclic Aromatic Hydrocarbons in Low-Temperature Environments via Successive Ethynyl Radical Additions Mebel, Alexander M.; Kislov, Vadim V.; Kaiser, Ralf I. Journal of the American Chemical Society, Vol. 130, Issue 41 https://doi.org/10.1021/ja804198a	journal	October 2008
Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study Kislov, V. V.; Nguyen, T. L.; Mebel, A. M. The Journal of Chemical Physics, Vol. 120, Issue 15 https://doi.org/10.1063/1.1676275	journal	April 2004
Detailed Chemical Modeling of the Circumstellar Envelopes of Carbon Stars: Application to IRC +10216 Doty, Steven D.; Leung, Chun Ming The Astrophysical Journal, Vol. 502, Issue 2 https://doi.org/10.1086/305911	journal	August 1998
A Barrierless Pathway Accessing the C9H9 and C9H8 Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl Thomas, Aaron M.; Doddipatla, Srinivas; Kaiser, Ralf I. Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-53987-5	journal	November 2019
Addition and cyclization reactions in the thermal conversion of hydrocarbons with enyne structure, II. Analysis of radicals and carbenes from ethynylbenzene Guthier, Klaus; Hebgen, Peter; Homann, Klaus-Heinrich Liebigs Annalen, Vol. 1995, Issue 4 https://doi.org/10.1002/jlac.199519950489	journal	April 1995
Elucidating the Formation of Ethynylbutatrienylidene (HCCCHCCC; X¹A′) in the Taurus Molecular Cloud (TMC-1) via the Gas-phase Reaction of Tricarbon (C₃) with the Propargyl Radical (C₃H₃) Mebel, Alexander M.; Agúndez, Marcelino; Cernicharo, José The Astrophysical Journal Letters, Vol. 945, Issue 2 https://doi.org/10.3847/2041-8213/acbf41	journal	March 2023
Gas-phase synthesis of benzene via the propargyl radical self-reaction Zhao, Long; Lu, Wenchao; Ahmed, Musahid Science Advances, Vol. 7, Issue 21 https://doi.org/10.1126/sciadv.abf0360	journal	May 2021
Observation of a free radical during the photolysis of phenyliodoacetylene Coleman, J. S.; Hudson, A.; Root, K. D. J. Chemical Physics Letters, Vol. 11, Issue 3 https://doi.org/10.1016/0009-2614(71)80491-8	journal	October 1971
A crossed molecular beams study of the reaction of dicarbon molecules with benzene Gu, Xibin; Guo, Ying; Zhang, Fangtong Chemical Physics Letters, Vol. 436, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.12.094	journal	February 2007
A high‐intensity multi‐purpose piezoelectric pulsed molecular beam source Proch, D.; Trickl, T. Review of Scientific Instruments, Vol. 60, Issue 4 https://doi.org/10.1063/1.1141006	journal	April 1989
A crossed molecular beams study of the reaction of the ethynyl radical (C2H(X2Σ+)) with allene (H2CCCH2(X1A1)) Zhang, Fangtong; Kim, Seol; Kaiser, Ralf I. Physical Chemistry Chemical Physics, Vol. 11, Issue 23 https://doi.org/10.1039/b822366a	journal	January 2009
Detailed modeling of soot formation in laminar premixed ethylene flames at a pressure of 10 bar Kazakov, Andrei; Wang, Hai; Frenklach, Michael Combustion and Flame, Vol. 100, Issue 1-2 https://doi.org/10.1016/0010-2180(94)00086-8	journal	January 1995
Formation and growth mechanisms of polycyclic aromatic hydrocarbons: A mini-review Reizer, Edina; Viskolcz, Béla; Fiser, Béla Chemosphere, Vol. 291 https://doi.org/10.1016/j.chemosphere.2021.132793	journal	March 2022
Interstellar Polycyclic Aromatic Hydrocarbon Molecules Tielens, A. G. G. M. Annual Review of Astronomy and Astrophysics, Vol. 46, Issue 1 https://doi.org/10.1146/annurev.astro.46.060407.145211	journal	September 2008
Small hydrocarbon molecules in cloud-forming brown dwarf and giant gas planet atmospheres Bilger, C.; Rimmer, P.; Helling, Ch. Monthly Notices of the Royal Astronomical Society, Vol. 435, Issue 3 https://doi.org/10.1093/mnras/stt1378	journal	September 2013
Discrimination of product isomers in the photodissociation of propyne and allene at 193 nm Sun, Weizhong; Yokoyama, Keiichi; Robinson, Jason C. The Journal of Chemical Physics, Vol. 110, Issue 9 https://doi.org/10.1063/1.478318	journal	March 1999
Kinetic Study of the OH Radical Reaction with Phenylacetylene Abhinavam Kailasanathan, Ranjith Kumar; Thapa, Juddha; Goulay, Fabien The Journal of Physical Chemistry A, Vol. 118, Issue 36 https://doi.org/10.1021/jp506160p	journal	August 2014
Gaussian-3 (G3) theory for molecules containing first and second-row atoms Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. The Journal of Chemical Physics, Vol. 109, Issue 18 https://doi.org/10.1063/1.477422	journal	November 1998
Gaussian-3 theory using density functional geometries and zero-point energies Baboul, Anwar G.; Curtiss, Larry A.; Redfern, Paul C. The Journal of Chemical Physics, Vol. 110, Issue 16 https://doi.org/10.1063/1.478676	journal	April 1999
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) Kaiser, R. I.; Chiong, C. C.; Asvany, O. The Journal of Chemical Physics, Vol. 114, Issue 8 https://doi.org/10.1063/1.1330233	journal	February 2001
Chemical speciation and soot measurements in laminar counterflow diffusion flames of ethylene and ammonia mixtures Zhou, Mengxiang; Yan, Fuwu; Ma, Liuhao Fuel, Vol. 308 https://doi.org/10.1016/j.fuel.2021.122003	journal	January 2022
A comparative study on soot and PAH formation of C10 naphthenic ring-containing species in laminar coflow diffusion flames Gao, Zhan; Cheng, Xiaogang; Ren, Fei Fuel, Vol. 332 https://doi.org/10.1016/j.fuel.2022.125893	journal	January 2023
PAH Growth Initiated by Propargyl Addition: Mechanism Development and Computational Kinetics Raj, Abhijeet; Al Rashidi, Mariam J.; Chung, Suk Ho The Journal of Physical Chemistry A, Vol. 118, Issue 16 https://doi.org/10.1021/jp410704b	journal	April 2014

Similar Records

Elucidating the Chemical Dynamics of the Elementary Reactions of the 1-Propynyl Radical (CH₃CC; X²A₁) with Methylacetylene (H₃CCCH; X¹A₁) and Allene (H₂CCCH₂; X¹A₁)

Journal Article · Sun Jun 09 00:00:00 EDT 2019 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1988095

He, Chao; Zhao, Long; Thomas, Aaron M.; +3 more

A combined crossed molecular beams and computational study on the formation of distinct resonantly stabilized C₅H₃ radicals via chemically activated C₅H₄ and C₆H₆ intermediates

Journal Article · Thu Mar 08 00:00:00 EST 2018 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1988095

Thomas, Aaron M.; Lucas, Michael; Zhao, Long; +3 more

Identification of C₅H_x Isomers in Fuel-Rich Flames by Photoionization Mass Spectrometry and Electronic Structure Calculations

Journal Article · Tue Mar 07 00:00:00 EST 2006 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1988095

Hansen, Nils; Klippenstein, Stephen J.; Miller, James A.; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Allenes
Chemical reactions
Energy
Hydrocarbons
Hydrogen

Title: Exploring the Chemical Dynamics of Phenylethynyl Radical (C 6 H 5 CC; X 2 A 1 ) Reactions with Allene (H 2 CCCH 2 ; X 1 A 1 ) and Methylacetylene (CH 3 CCH; X 1 A 1 )

Citation Formats

References (47)

Similar Records

Related Subjects

Title: Exploring the Chemical Dynamics of Phenylethynyl Radical (C ₆ H ₅ CC; X ² A ₁ ) Reactions with Allene (H ₂ CCCH ₂ ; X ¹ A ₁ ) and Methylacetylene (CH ₃ CCH; X ¹ A ₁ )