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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:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]
  1. Univ. of Hawaii, Honolulu, HI (United States). Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  3. Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
  4. Florida Intl Univ., Miami, FL (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Florida International Univ., 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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1561947
Alternate Identifier(s):
OSTI ID: 1594727; OSTI ID: 1603225
Grant/Contract Number:  
AC02-05CH11231; FG02-04ER15570; FG02-03ER15411
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
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 States: N. p., 2019. Web. doi:10.1038/s41467-019-11652-5.
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 States. doi:10.1038/s41467-019-11652-5.
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 States. doi:10.1038/s41467-019-11652-5. https://www.osti.gov/servlets/purl/1561947.
@article{osti_1561947,
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},
issn = {2041-1723},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {8}
}

Journal Article:
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Figures / Tables:

Fig. 1 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 » reactants; energies in square brackets are defined with respect to the 1- methylindenyl radical; all energies for the (partially) deuterated species are within 1-2 kJ mol−1 of the non-deuterated counterparts. All energies are given in kJ mol−1. The detailed potential energy surfaces and coordinates or reactants, intermediates, and products are compiled in the Supplementary Figs. 1 and 2, and Supplementary Note 2« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.