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Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d0cp03846f· OSTI ID:1814910
 [1];  [1];  [2];  [2];  [2];  [3];  [3];  [4];  [4];  [5];  [6];  [6]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Samara National Research Univ. (Russia)
  4. Samara National Research Univ. (Russia); Lebedev Physical Inst., Samara (Russia)
  5. Samara National Research Univ. (Russia); Florida International Univ., Miami, FL (United States)
  6. Florida International Univ., Miami, FL (United States)
+ Show Author Affiliations
The tricyclic polycyclic aromatic hydrocarbons (PAHs) 3H-cyclopenta[a]naphthalene (C13H10), 1H-cyclopenta[b]naphthalene (C13H10) and 1H-cyclopenta[a]naphthalene (C13H10) along with their indene-based bicyclic isomers (E)-5-(but-1-en-3-yn-1-yl)-1H-indene, (E)-6-(but-1-en-3-yn-1-yl)-1H-indene, 5-(but-3-ene-1-yn-1-yl)-1H-in-dene, and 6-(but-3-ene-1-yn-1-yl)-1H-indene were formed via a “directed synthesis” in a high-temperature chemical micro reactor at the temperature of 1300 ± 10 K through the reactions of the 5- and 6-indenyl radicals (C9H7˙) with vinylacetylene (C4H4). The isomer distributions were probed utilizing tunable vacuum ultraviolet light by recording the photoionization efficiency curves at mass-to-charge of m/z = 166 (C13H10) and 167 (13CC12H10) of the products in a supersonic molecular beam. Here, the underlying reaction mechanisms involve the initial formation of van-der-Waals complexes followed by addition of the 5- and 6-indenyl radicals to vinylacetylene via submerged barriers, followed by isomerization (hydrogen shifts, ring closures), and termination via atomic hydrogen elimination accompanied by aromatization. All the barriers involved in the formation of 3H-cyclopenta[a]naphthalene, 1H-cyclopenta[b]naphthalene and 1H-cyclopenta[a]naphthalene are submerged with respect to the reactants indicating that the mechanisms are in fact barrierless, potentially forming PAHs via the hydrogen abstraction – vinylacetylene addition (HAVA) pathway in the cold molecular clouds such as Taurus Molecular Cloud-1 (TMC-1) at temperatures as low as 10 K.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1814910
Alternate ID(s):
OSTI ID: 1669154
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 39 Vol. 22; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Hydrogen-Abstraction/Acetylene-Addition Exposed journal October 2016
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
Selective Formation of Indene through the Reaction of Benzyl Radicals with Acetylene journal April 2015
Gaussian-3 theory using coupled cluster energies journal November 1999
Formation mechanism of polycyclic aromatic hydrocarbons and fullerenes in premixed benzene flames journal October 1999
Titan's surface reviewed: the nature of bright and dark terrain journal August 1997
Composition profiles and reaction mechanisms in a near-sooting premixed benzene/oxygen/argon flame journal January 1981
Effect of fuel structure on pathways to soot journal January 1988
Experimental study of PAH formation in laminar counterflow CH4N2/O2N2 and C3H8N2/O2N2 nonpremixed flames journal July 2005
Improved sooting tendency measurements for aromatic hydrocarbons and their implications for naphthalene formation pathways journal March 2007
Photoionization cross sections for reaction intermediates in hydrocarbon combustion journal December 2005
PAH emissions from high-temperature oxidation of vaporized anthracene journal January 2007
Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry journal January 2013
DFT study of five-membered ring PAHs journal April 2020
Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames journal January 2017
Functional Relationships between Kinetic, Flow, and Geometrical Parameters in a High-Temperature Chemical Microreactor journal October 2018
VUV Photoionization Study of the Formation of the Simplest Polycyclic Aromatic Hydrocarbon: Naphthalene (C 10 H 8 ) journal May 2018
Soot formation in binary hydrocarbon mixtures journal July 1988
Reaction of Phenyl Radicals with Propyne journal February 2002
High Pressure Pyrolysis of Toluene. 2. Modeling Benzyl Decomposition and Formation of Soot Precursors journal August 2006
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
An Ab Initio G3-Type/Statistical Theory Study of the Formation of Indene in Combustion Flames. II. The Pathways Originating from Reactions of Cyclic C 5 SpeciesCyclopentadiene and Cyclopentadienyl Radicals journal January 2008
A VUV Photoionization Study of the Combustion-Relevant Reaction of the Phenyl Radical (C 6 H 5 ) with Propylene (C 3 H 6 ) in a High Temperature Chemical Reactor journal March 2012
Crossed Molecular Beams Study on the Formation of Vinylacetylene in Titan’s Atmosphere † journal October 2009
A VUV Photoionization Study of the Formation of the Indene Molecule and Its Isomers journal June 2011
Gas phase synthesis of [4]-helicene journal April 2019
Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions journal August 2019
Pyrene synthesis in circumstellar envelopes and its role in the formation of 2D nanostructures journal March 2018
Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere journal October 2018
A VUV photoionization study of the multichannel reaction of phenyl radicals with 1,3-butadiene under combustion relevant conditions journal January 2013
Formation of 5- and 6-methyl-1H-indene (C 10 H 10 ) via the reactions of the para-tolyl radical (C 6 H 4 CH 3 ) with allene (H 2 CCCH 2 ) and methylacetylene (HCCCH 3 ) under single collision conditions journal January 2015
Ring-annelated corannulenes as fullerene receptors. A DFT-D study journal January 2014
A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene – toward the formation of methylnaphthalenes journal January 2015
How to add a five-membered ring to polycyclic aromatic hydrocarbons (PAHs) – molecular mass growth of the 2-naphthyl radical (C 10 H 7 ) to benzindenes (C 13 H 10 ) as a case study journal January 2019
Reactions of chemically activated C9H9 species. journal April 2002
Reactions of chemically activated C9H9 species II: The reaction of phenyl radicals with allene and cyclopropene, and of benzyl radicals with acetyleneElectronic supplementary information (ESI) available: Full [C9H9] reaction scheme. Additional quantum chemical calculations not reported yet in earlier publications. Full product distribution and over-all rate coefficient listings, both uncorrected and effective data, for all reaction conditions examined. For the most important products, tables are included listing the yield as function of temperature and pressure. Modified Arrhenius fits for the over-all TST rate coefficient and the TST rate coefficient of the different entrance channels are listed for different temperature intervals. See http://www.rsc.org/suppdata/cp/b3/b303908k/ or contact the authors directly, or download from the website http://arrhenius.chem.kuleuven.ac.be. journal January 2003
Formation of the diphenyl molecule in the crossed beam reaction of phenyl radicals with benzene journal February 2008
Gaussian-3 (G3) theory for molecules containing first and second-row atoms journal November 1998
Gaussian-3 theory using density functional geometries and zero-point energies journal April 1999
Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium journal December 2011
The properties of a micro-reactor for the study of the unimolecular decomposition of large molecules journal September 2014
Fullerenes, fulleranes and polycyclic aromatic hydrocarbons in the Allende meteorite journal July 1997

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