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Abstract Recent detections of aromatic species in dark molecular clouds suggest that formation pathways may be efficient at very low temperatures and pressures, yet current astrochemical models are unable to account for their derived abundances, which can often deviate from model predictions by several orders of magnitude. The propargyl radical, a highly abundant species in the dark molecular cloud TMC-1, is an important aromatic precursor in combustion flames and possibly interstellar environments. We performed astrochemical modeling of TMC-1 using the three-phase gas-grain codeNAUTILUSand an updated chemical network, focused on refining the chemistry of the propargyl radical and related species. The abundance of the propargyl radical has been increased by half an order of magnitude compared to the previous GOTHAM network. This brings it closer in line with observations, but it remains underestimated by 2 orders of magnitude compared to its observed value. Predicted abundances for the chemically related C4H3N isomers within an order of magnitude of observed values corroborate the high efficiency of CN addition to closed-shell hydrocarbons under dark molecular cloud conditions. The results of our modeling provide insight into the chemical processes of the propargyl radical in dark molecular clouds and highlight the importance of resonance-stabilized radicals in polycyclic aromatic hydrocarbon formation.
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Is Phenylnitrene a Missing Link in the Formation of Polycyclic Aromatic Nitrogen Heterocycles?
Abstract The incorporation of heteroatoms into the framework of polycyclic aromatic hydrocarbons (PAHs), in particular of nitrogen to yield polycyclic aromatic nitrogen heterocycles (PANHs), has been proposed for both astronomical and combustion environments, but no suitable precursors and pathways have been found. Analogous pathways to PAH formation are kinetically or energetically inhibited in the presence of a nitrogen heteroatom. We report on the reaction of phenylnitrene (3PhN,c‐C6H5N) with resonance‐stabilized propargyl radicals (C3H3) and find that the association reaction bifurcates depending on the orientation of the attacking propargyl radical and yields multiple isomeric products. Among them, we identify the condensed‐ring quinoline and conclude that nitrenes are viable candidates to drive the formation of PANHs.
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- Award ID(s):
- 2308045
- PAR ID:
- 10610608
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 64
- Issue:
- 31
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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