Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Unconventional gas-phase preparation of the prototype polycyclic aromatic hydrocarbon naphthalene (C10H8) via the reaction of benzyl (C7H7) and propargyl (C3H3) radicals coupled with hydrogen-atom assisted isomerization

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/d3sc00911d· OSTI ID:1972235
 [1];  [1];  [2];  [2];  [3];  [4];  [5];  [5];  [6];  [6]
  1. University of Hawai'i at Mānoa, Honolulu, HI (United States)
  2. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  3. Lebedev Physical Institute, Samara (Russian Federation); Samara National Research University (Russian Federation)
  4. Samara National Research University (Russian Federation)
  5. Lebedev Physical Institute, Samara (Russian Federation)
  6. Florida International University, Miami, FL (United States)
+ Show Author Affiliations
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium and in meteorites such as Murchison and Allende and signify the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles (soot particles, interstellar grains). However, the predicted lifetime of interstellar PAHs of some 108 years imply that PAHs should not exist in extraterrestrial environments suggesting that key mechanisms of their formation are elusive. Exploiting a microchemical reactor and coupling these data with computational fluid dynamics (CFD) simulations and kinetic modeling, we reveal through an isomer selective product detection that the reaction of the resonantly stabilized benzyl (C7H7) and the propargyl (C3H3) synthesizes the simplest representative of PAHs – the 10π Hückel aromatic naphthalene (C10H8) molecule – via the novel Propargyl Addition–BenzAnnulation (PABA) mechanism. The gas-phase preparation of naphthalene affords a versatile concept of the reaction of combustion and astronomically abundant propargyl radicals with aromatic radicals carrying the radical center at the methylene moiety (aromatic-CH2) as a previously passed over source of aromatics in high temperature environments thus bringing us closer to an understanding of the aromatic universe we live in.
Research Organization:
Florida International University (FIU), Miami, FL (United States); Florida International University, Miami, FL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of Hawai'i at Mānoa, Honolulu, HI (United States)
Sponsoring Organization:
Ministry of Higher Education and Science of the Russian Federation; Ministry of Science and Higher Education of the Russian Federation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231; FG02-03ER15411; FG02-04ER15570
OSTI ID:
1972235
Alternate ID(s):
OSTI ID: 2371718
OSTI ID: 1975327
OSTI ID: 2997069
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 20 Vol. 14; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (49)

Theoretical study of the thermal isomerization of fulvene to benzene journal December 1996
Computational study on the recombination reaction between benzyl and propargyl radicals journal January 2012
Benzene and its isomers: How many structures can we draw for C6H6? journal May 2001
Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels journal October 1992
Organic compounds in the Forest Vale, H4 ordinary chondrite journal July 1992
Unimolecular reaction mechanisms involving C3H4, C4H4, and C6H6 hydrocarbon species journal January 1992
Detailed kinetic modeling of soot formation in shock-tube pyrolysis of acetylene journal January 1985
On the driving force of PAH production journal January 1989
Molecular-growth pathways in premixed flames of benzene and toluene doped with propyne journal September 2022
Studies of aromatic hydrocarbon formation mechanisms in flames: Progress towards closing the fuel gap journal January 2006
Hydrogen-assisted isomerizations of fulvene to benzene and of larger cyclic aromatic hydrocarbons journal January 2013
Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry journal January 2013
The non-destructive separation of diverse astrobiologically relevant organic molecules by customizable capillary zone electrophoresis and monolithic capillary electrochromatography journal May 2019
An Aromatic Universe–A Physical Chemistry Perspective journal April 2021
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
The Recombination of Propargyl Radicals:  Solving the Master Equation journal August 2001
The Recombination of Propargyl Radicals and Other Reactions on a C 6 H 6 Potential journal October 2003
Exploration of C 6 H 6 Potential Energy Surface:  A Computational Effort to Unravel the Relative Stabilities and Synthetic Feasibility of New Benzene Isomers † journal December 2004
An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C 11 H 10 /C 11 H 3 D 7 ) in the Reactions of the Para-Tolyl (C 7 H 7 ) and Para-Tolyl-d7 (C 7 D 7 ) with Vinylacetylene (C 4 H 4 ) journal April 2014
Theoretical Study on the Mechanism of the Dissociation of Benzene. The C 5 H 3 + CH 3 Product Channel journal September 1997
Unconventional excited-state dynamics in the concerted benzyl (C7H7) radical self-reaction to anthracene (C14H10) journal February 2022
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
Pressure-dependent rate constants for PAH growth: formation of indene and its conversion to naphthalene journal January 2016
Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites journal January 2022
Reaction mechanism of soot formation in flames journal February 2002
Formation and consumption of single-ring aromatic hydrocarbons and their precursors in premixed acetylene, ethylene and benzene flamesElectronic supplementary information (ESI) available: Thermodynamic and kinetic property data. See http://www.rsc.org/suppdata/cp/b1/b110089k/ journal April 2002
Carbon molecules in space: from astrochemistry to astrobiology journal January 2006
Polycyclic aromatic hydrocarbon processing in interstellar shocks journal February 2010
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 journal March 2021
Flash pyrolysis nozzle for generation of radicals in a supersonic jet expansion journal August 1992
Ab initio molecular orbital/Rice–Ramsperger–Kassel–Marcus theory study of multichannel rate constants for the unimolecular decomposition of benzene and the H+C6H5 reaction over the ground electronic state journal May 2001
Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study journal April 2004
The chemistry in circumstellar envelopes of evolved stars: Following the origin of the elements to the origin of life journal August 2006
Charged polycyclic aromatic hydrocarbon clusters and the galactic extended red emission journal March 2007
High molecular diversity of extraterrestrial organic matter in Murchison meteorite revealed 40 years after its fall journal February 2010
Formation of resonantly stabilised free radicals via the reactions of atomic carbon, dicarbon, and tricarbon with unsaturated hydrocarbons: theory and crossed molecular beams experiments journal October 2015
Considerations Regarding Interstellar Molecules journal July 1937
Formation of polycyclic aromatic hydrocarbons in circumstellar envelopes journal June 1989
Polycyclic aromatic hydrocarbon formation in carbon-rich stellar envelopes journal December 1992
Mid-infrared spectra of WC 9 stars - The composition of circumstellar and interstellar dust journal September 1989
Gas-phase synthesis of benzene via the propargyl radical self-reaction journal May 2021
Intrtstellar Polycyclic Aromatic Hydrocarbons and Carbon in Interplanetary Dust Particles and Meteorites journal July 1987
Detection of two interstellar polycyclic aromatic hydrocarbons via spectral matched filtering journal March 2021
Formation of Two-ring Polycyclic Aromatic Hydrocarbons via the Recombination of Benzyl and Propargyl Radicals under the Circumstellar Envelopes Conditions of Asymptotic Giant Branch Stars journal September 2022
Complex Organic Interstellar Molecules journal September 2009
Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium journal April 2015
A New Component of the Interstellar Matter: Small Grains and Large Aromatic Molecules journal September 1989
Interstellar Polycyclic Aromatic Hydrocarbon Molecules journal September 2008

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY