Conversion of acenaphthalene to phenalene via methylation: A theoretical study

Porfiriev, Denis P.; Azyazov, Valeriy N.; Mebel, Alexander M.

doi:10.1016/j.combustflame.2019.11.038

Conversion of acenaphthalene to phenalene via methylation: A theoretical study

Journal Article · Wed Dec 18 23:00:00 EST 2019 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2019.11.038· OSTI ID:1766436

Porfiriev, Denis P. ^[1]; Azyazov, Valeriy N. ^[2]; Mebel, Alexander M. ^[3]

Samara National Research Univ. (Russia); Lebedev Physical Inst., Samara (Russia); Florida International University
Samara National Research Univ. (Russia); Lebedev Physical Inst., Samara (Russia)
Samara National Research Univ. (Russia); Florida International Univ., Miami, FL (United States)

Ab initio calculations of the C₁₃H₁₀ and C₁₃H₉ potential energy surfaces related to the reaction of 1-acenaphthyl and methyl radicals and secondary isomerization of C₁₃H₉ primary radical products have been performed at the chemically accurate G3(MP2,CC)//B3LYP/6-311G** level of theory to unravel the mechanism of conversion of acenaphthalene to phenalene or phenalenyl radical + H. The computed energetics and molecular parameters were utilized in Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of reaction rate constants and relative product yields. The 1-acenaphthyl + CH₃ reaction is predicted to proceed by a fast radical-radical recombination mechanism and to predominantly produce collisionally stabilized 1-methylacenaphthalene B1 or a C₁₃H₉ benzylic radical A1 + H with exothermicities of 106.8 and 25.2 kcal/mol, respectively. The A1 + H channel is preferable at higher temperatures, whereas the stabilization of 1-methylacenaphthalene is favored at higher pressures. The radical A1 can nearly irreversibly interconvert to phenalenyl radical AP via a 22.7 kcal/mol exothermic isomerization process involving formal insertion of the CH₂ group into a C-C bond of the five-member ring leading to the expansion of this ring to a six-member ring. The rate constants for the H addition reaction to phenalenyl radical to form phenalene and the reverse H loss from phenalene were also computed and the strength of the weakest C-H bond in the CH₂ group of phenalene is evaluated as 62.2 kcal/mol. The analysis of the reaction kinetics allowed us to deduce a mechanism for the conversion of 1-acenaphthyl radical to phenalene or phenalenyl radical + H via methylation involving the formation of A1 via a well-skipping channel or stabilization and dissociation of (or H abstraction from) B1 followed by isomerization of A1 to phenalenyl AP, which can add an H atom producing phenalene. As a result, rate constants for the significant elementary reactions are fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the expansion of a five-member ring on a zigzag edge of PAH to a six-member ring by methylation.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Ministry of Science and Higher Education of the Russian Federation

Grant/Contract Number:: FG02-04ER15570

OSTI ID:: 1766436

Alternate ID(s):: OSTI ID: 1702324

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Vol. 213; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Conversion of acenaphthalene to phenalene via methylation: A theoretical study

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