Molecular weight growth by the phenyl&nbsp;+&nbsp;cyclopentadienyl reaction: Well-skipping, ring-opening, and dissociation

Couch, David E.; Jasper, Ahren W.; Kukkadapu, Goutham; San Marchi, Myrsini M.; Zhang, Angie J.; Taatjes, Craig A.; Hansen, Nils

doi:10.1016/j.combustflame.2022.112439

Molecular weight growth by the phenyl + cyclopentadienyl reaction: Well-skipping, ring-opening, and dissociation

Journal Article · Thu Nov 03 00:00:00 EDT 2022 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2022.112439· OSTI ID:2474922

^[1]; Jasper, Ahren W. ^[2]; Kukkadapu, Goutham ^[3]; ^[1]; Zhang, Angie J. ^[1]; Taatjes, Craig A. ^[1]; Hansen, Nils ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Radical-radical reactions contribute to molecular weight growth of polycyclic aromatic hydrocarbons (PAHs), but their role is not well understood. The phenyl (Ph, C₆H₅) + cyclopentadienyl (C₅H₅) reaction has not been studied but can serve as a surrogate reaction for many reactions of larger aryl-σ radicals with resonance-stabilized π-radicals. The adducts of these reactions easily lose an H atom to produce a new π-radical. Here, through a combination of dilute flash pyrolysis experiments, theory, and simulation, we find that for the title reaction, substantial Ph—C₅H₄ + H is formed, dominantly by a well-skipping pathway, at conditions around 30 Torr and 1400 K. This radical is thermally stable at moderate temperatures but decomposes at higher temperatures following ring opening of the 5-member ring. Products corresponding to the loss of H, C₂H₂, and C₃H₃ are observed experimentally. Calculation of the C₁₁H₉ potential energy surface affirms that these are expected decomposition products and reveals multiple possible pathways.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC02-06CH11357; AC52-07NA27344; NA0003525

OSTI ID:: 2474922

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Vol. 257; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cyclopentadienyl radical
flash pyrolysis
polycyclic aromatic hydrocarbons (PAH)
radical-radical reactions
ring opening
well-skipping

Molecular weight growth by the phenyl + cyclopentadienyl reaction: Well-skipping, ring-opening, and dissociation

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