A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons
Abstract
The hydrogen-abstraction/acetylene-addition mechanism has been fundamental to unravelling the synthesis of polycyclic aromatic hydrocarbons (PAHs) detected in combustion flames and carbonaceous meteorites like Orgueil and Murchison. However, the fundamental reaction pathways accounting for the synthesis of complex PAHs, such as the tricyclic anthracene and phenanthrene along with their dihydrogenated counterparts, remain elusive to date. By investigating the hitherto unknown chemistry of the 1-naphthyl radical with 1,3-butadiene, we reveal a facile barrierless synthesis of dihydrophenanthrene adaptable to low temperatures. Finally, these aryl-type radical additions to conjugated hydrocarbons via resonantly stabilized free-radical intermediates defy conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and thus may represent an overlooked path to PAHs as complex as coronene and corannulene in cold regions of the interstellar medium like in the Taurus Molecular Cloud.
- Authors:
-
[1];
[1];
[2]
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Florida International Univ., Miami, FL (United States)
- Publication Date:
- Research Org.:
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1602964
- Alternate Identifier(s):
- OSTI ID: 1373978
- Grant/Contract Number:
- FG02-03ER15411; FG02-04ER15570
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemPhysChem
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 15; Journal ID: ISSN 1439-4235
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aryl radicals; astrochemistry; gas phase chemistry; mass spectrometry; polycyclic aromatic hydrocarbon
Citation Formats
Thomas, Aaron M., Lucas, Michael, Yang, Tao, Kaiser, Ralf I., Fuentes, Luis, Belisario-Lara, Daniel, and Mebel, Alexander M. A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons. United States: N. p., 2017.
Web. doi:10.1002/cphc.201700515.
Thomas, Aaron M., Lucas, Michael, Yang, Tao, Kaiser, Ralf I., Fuentes, Luis, Belisario-Lara, Daniel, & Mebel, Alexander M. A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons. United States. https://doi.org/10.1002/cphc.201700515
Thomas, Aaron M., Lucas, Michael, Yang, Tao, Kaiser, Ralf I., Fuentes, Luis, Belisario-Lara, Daniel, and Mebel, Alexander M. Sun .
"A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons". United States. https://doi.org/10.1002/cphc.201700515. https://www.osti.gov/servlets/purl/1602964.
@article{osti_1602964,
title = {A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons},
author = {Thomas, Aaron M. and Lucas, Michael and Yang, Tao and Kaiser, Ralf I. and Fuentes, Luis and Belisario-Lara, Daniel and Mebel, Alexander M.},
abstractNote = {The hydrogen-abstraction/acetylene-addition mechanism has been fundamental to unravelling the synthesis of polycyclic aromatic hydrocarbons (PAHs) detected in combustion flames and carbonaceous meteorites like Orgueil and Murchison. However, the fundamental reaction pathways accounting for the synthesis of complex PAHs, such as the tricyclic anthracene and phenanthrene along with their dihydrogenated counterparts, remain elusive to date. By investigating the hitherto unknown chemistry of the 1-naphthyl radical with 1,3-butadiene, we reveal a facile barrierless synthesis of dihydrophenanthrene adaptable to low temperatures. Finally, these aryl-type radical additions to conjugated hydrocarbons via resonantly stabilized free-radical intermediates defy conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and thus may represent an overlooked path to PAHs as complex as coronene and corannulene in cold regions of the interstellar medium like in the Taurus Molecular Cloud.},
doi = {10.1002/cphc.201700515},
journal = {ChemPhysChem},
number = 15,
volume = 18,
place = {United States},
year = {Sun May 28 00:00:00 EDT 2017},
month = {Sun May 28 00:00:00 EDT 2017}
}
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