Bay capping via acetylene addition to polycyclic aromatic hydrocarbons: Mechanism and kinetics

Tuli, Lotefa Binta; Mebel, Alexander M.; Frenklach, Michael

doi:10.1016/j.proci.2022.08.018

Bay capping via acetylene addition to polycyclic aromatic hydrocarbons: Mechanism and kinetics

Journal Article · Sun Oct 02 00:00:00 EDT 2022 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2022.08.018· OSTI ID:2419004

Tuli, Lotefa Binta ^[1]; ^[2]; ^[3]

Florida International Univ. (FIU), Miami, FL (United States); OSTI
Florida International Univ. (FIU), Miami, FL (United States)
Univ. of California, Berkeley, CA (United States)

The bay-capping mechanism on PAH armchair edges and the kinetics of acetylene addition to 6–6–5 and 5–6–5 bays have been explored by ab initio/RRKM-ME calculations. The bays on the edges were modeled by C₂₁H₁₁ and C₂₀H₉ radicals produced by H abstractions from 7H-benzo[c]cyclopenta[e]pyrene and dicyclopenta[cf]pyrene. The C₂₀H₉ + C₂H₂ reaction is shown to have a low entrance barrier and to rapidly form the capped product, indaceno[2,1,8,7-cdefg]pyrene, along with ethynyl substituted dicyclopenta[cf]pyrene at temperatures above 1400 K. The reactivity of C₂₁H₁₁ is shown to be governed by the location of the unpaired electron; the π radical R1 formed by H abstraction from the CH₂ group in 7H-benzo[c]cyclopenta[e]pyrene reacts with C₂H₂ very slowly owing to a high entrance barrier, with the bay-capping rate constant approaching 10^-16 cm³ molecule^-1 s^-1 only at temperatures above 2000K. Further, this result reaffirms that the growth of π aryl radicals via acetylene addition is inefficient and reflects the generally low reactivity of such radicals where the spin density is highly delocalized over the entire polyaromatic system. Alternatively, the σ C₂₁H₁₁ radical R2 produced by H abstraction from the five-membered ring at the bay rapidly reacts with C₂H₂ forming the bay-capped product, with the rate constant on the order of 10^-12 cm³ molecule^-1 s^-1 at T≥1500K. Rate constants for the capping reactions at the 6–6–5 and 5–6–5 bays are compared with those at the 6–0–6, 6–6–6, and 6–5–6 bays. The site-specific bay-capping rate constants have been utilized in kMC simulations of the PAH growth and the results showed measurable differences when the 6–6–5 and 5–6–5 bay-capping reactions are taken into account, including an increase of the growth rate and the formation of closed-shell PAH and a rise of the number of embedded five-membered rings accompanied with a slight decrease of their overall amount.

View Accepted Manuscript (DOE)

Research Organization:: Florida International Univ. (FIU), Miami, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-04ER15570

OSTI ID:: 2419004

Alternate ID(s):: OSTI ID: 1984145

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 39; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Hydrogen-Abstraction/C2H2-Addition (HACA)
PAH growth
Reaction mechanism
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Bay capping via acetylene addition to polycyclic aromatic hydrocarbons: Mechanism and kinetics

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