Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions

Zhao, Long; Kaiser, Ralf. I.; Lu, Wenchao; Xu, Bo; Ahmed, Musahid; Morozov, Alexander N.; Mebel, Alexander M.; Howlader, A. Hasan; Wnuk, Stanislaw F.

doi:10.1038/s41467-019-11652-5

Title: Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions

Abstract

Polycyclic aromatic hydrocarbons (PAHs) represent key molecular building blocks leading to carbonaceous nanoparticles identified in combustion systems and extraterrestrial environments. However, the understanding of their formation and growth in these high temperature environments has remained elusive. We present a mechanism through laboratory experiments and computations revealing how the prototype PAH—naphthalene—can be efficiently formed via a rapid 1-indenyl radical—methyl radical reaction. This versatile route converts five- to six-membered rings and provides a detailed view of high temperature mass growth processes that can eventually lead to graphene-type PAHs and two-dimensional nanostructures providing a radical new view about the transformations of carbon in our universe.

Authors:

;

; Morozov, Alexander N.;

;

Publication Date:: Thu Aug 15 00:00:00 EDT 2019

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Florida International Univ. (FIU), Miami, FL (United States); Univ. of Hawaii at Manoa, Honolulu, HI (United States)

Sponsoring Org.:: USDOE Office of Secretary of Energy (S); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1619682

Alternate Identifier(s):: OSTI ID: 1561947; OSTI ID: 1594727; OSTI ID: 1603225

Grant/Contract Number:: FG02-03ER15411; AC02-05CH11231; FG02-04ER15570

Resource Type:: Published Article

Journal Name:: Nature Communications

Additional Journal Information:: Journal Name: Nature Communications Journal Volume: 10 Journal Issue: 1; Journal ID: ISSN 2041-1723

Publisher:: Nature Publishing Group

Country of Publication:: United Kingdom

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats


                    Zhao, Long, Kaiser, Ralf. I., Lu, Wenchao, Xu, Bo, Ahmed, Musahid, Morozov, Alexander N., Mebel, Alexander M., Howlader, A. Hasan, and Wnuk, Stanislaw F. Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions.  United Kingdom: N. p., 2019. 
Web.  doi:10.1038/s41467-019-11652-5.

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                    Zhao, Long, Kaiser, Ralf. I., Lu, Wenchao, Xu, Bo, Ahmed, Musahid, Morozov, Alexander N., Mebel, Alexander M., Howlader, A. Hasan, & Wnuk, Stanislaw F. Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions.  United Kingdom.  https://doi.org/10.1038/s41467-019-11652-5

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                    Zhao, Long, Kaiser, Ralf. I., Lu, Wenchao, Xu, Bo, Ahmed, Musahid, Morozov, Alexander N., Mebel, Alexander M., Howlader, A. Hasan, and Wnuk, Stanislaw F. Thu .  
"Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions".  United Kingdom.  https://doi.org/10.1038/s41467-019-11652-5.

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@article{osti_1619682,

  title        = {Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions},

  author       = {Zhao, Long and Kaiser, Ralf. I. and Lu, Wenchao and Xu, Bo and Ahmed, Musahid and Morozov, Alexander N. and Mebel, Alexander M. and Howlader, A. Hasan and Wnuk, Stanislaw F.},

  abstractNote = {Polycyclic aromatic hydrocarbons (PAHs) represent key molecular building blocks leading to carbonaceous nanoparticles identified in combustion systems and extraterrestrial environments. However, the understanding of their formation and growth in these high temperature environments has remained elusive. We present a mechanism through laboratory experiments and computations revealing how the prototype PAH—naphthalene—can be efficiently formed via a rapid 1-indenyl radical—methyl radical reaction. This versatile route converts five- to six-membered rings and provides a detailed view of high temperature mass growth processes that can eventually lead to graphene-type PAHs and two-dimensional nanostructures providing a radical new view about the transformations of carbon in our universe.},

  doi          = {10.1038/s41467-019-11652-5},

  journal      = {Nature Communications},

  number       = 1,

  volume       = 10,

  place        = {United Kingdom},

  year         = {Thu Aug 15 00:00:00 EDT 2019},

  month        = {Thu Aug 15 00:00:00 EDT 2019}

}

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Fig. 1: Reaction pathways for the 1-indenyl—(D3-)methyl systems leading to (D2-)naphthalene with atoms in blue tracing the deuterium atoms. The blue and red numbers indicate the mass-to-charge ratios of the reactants, intermediates, and products in the 1-indenyl/D3-methyl and 1-indenyl/methyl systems, respectively. The energies are defined with respect to the separatedmore »

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Fig. 3 (p. 5)

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Similar Records

Title: Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions

Abstract

Citation Formats

Figures / Tables:

A combined ab initio and photoionization mass spectrometric study of polyynes in fuel-rich flames journal, January 2008

Pyrene synthesis in circumstellar envelopes and its role in the formation of 2D nanostructures journal, March 2018

PAH formation and soot morphology in flames of C4 fuels journal, January 2015

Studies of aromatic hydrocarbon formation mechanisms in flames: Progress towards closing the fuel gap journal, January 2006

A VUV Photoionization Study of the Formation of the Indene Molecule and Its Isomers journal, June 2011

Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation journal, June 1977

The molecular universe journal, July 2013

Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth journal, September 2018

On the kinetics of the C5H5+C5H5 reaction journal, January 2013

Chemical Evolution of Carbonaceous Material in Interstellar Clouds journal, January 2000

Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere journal, October 2018

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

Can the C 5 H 5 + C 5 H 5 → C 10 H 10 → C 10 H 9 + H/C 10 H 8 + H 2 Reaction Produce Naphthalene? An Ab Initio/RRKM Study journal, September 2009

Hydrogen-Abstraction/Acetylene-Addition Exposed journal, October 2016

Isotopic compositions of individual polycyclic aromatic hydrocarbons from the Murchison meteorite journal, July 1994

Hydrogen-assisted isomerizations of fulvene to benzene and of larger cyclic aromatic hydrocarbons journal, January 2013

Radical-Radical Reactions journal, October 1996

Investigating repetitive reaction pathways for the formation of polycyclic aromatic hydrocarbons in combustion processes journal, June 2017

The CH3+C5H5 reaction: A potential source of benene at high temperatures journal, January 1996

VUV Photoionization Study of the Formation of the Simplest Polycyclic Aromatic Hydrocarbon: Naphthalene (C 10 H 8 ) journal, May 2018

Interstellar graphite in meteorites: Isotopic compositions and structural properties of single graphite grains from Murchison journal, March 1995

Charged polycyclic aromatic hydrocarbon clusters and the galactic extended red emission journal, March 2007

A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames journal, July 1997

The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule journal, February 1981

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

The cycling of carbon into and out of dust journal, January 2014

Density‐functional thermochemistry. III. The role of exact exchange journal, April 1993

Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients journal, August 2011

Calculations of Rate Coefficients for the Chemically Activated Reactions of Acetylene with Vinylic and Aromatic Radicals journal, November 1994

Computed Rate Coefficients and Product Yields for c -C 5 H 5 + CH 3 → Products journal, August 2009

Kinetics of the Self Reaction of Cyclopentadienyl Radicals journal, February 2015

Unimolecular Dissociations and Free Radical Recombination Reactions journal, March 1952

Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames journal, January 2018

Indigenous Polycyclic Aromatic Hydrocarbons in Circumstellar Graphite Grains from Primitive Meteorites journal, July 1998

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal, January 1988

Multireference perturbation theory for large restricted and selected active space reference wave functions journal, April 2000

Isotopic evidence from an Antarctic carbonaceous chondrite for two reaction pathways of extraterrestrial PAH formation journal, December 2000

In Situ Discovery of Graphite with Interstellar Isotopic Signatures in a Chondrule-Free Clast in an L3 Chondrite journal, May 1998

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Calculational and Experimental Investigations of the Pressure Effects on Radical−Radical Cross Combination Reactions: C 2 H 5 + C 2 H 3 † journal, July 2007

The photofragmentation of naphthalene and azulene monocations in the energy range 7–22 eV journal, December 1992

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Association rate constants for reactions between resonance-stabilized radicals: C3H3 + C3H3, C3H3 + C3H5, and C3H5 + C3H5
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Anharmonic vibrational spectroscopy of polycyclic aromatic hydrocarbons (PAHs)
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Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions
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Pressure-dependent rate constants for PAH growth: formation of indene and its conversion to naphthalene
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Kinetics of the CH ₃ + C ₅ H ₅ Reaction: A Theoretical Study
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Hydrogen Abstraction/Acetylene Addition Revealed
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A new era for combustion research
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Polycyclic aromatic hydrocarbon processing in interstellar shocks
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Unexpected Chemistry from the Reaction of Naphthyl and Acetylene at Combustion-Like Temperatures
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Functional Relationships between Kinetic, Flow, and Geometrical Parameters in a High-Temperature Chemical Microreactor
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