Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association

Morozov, Alexander N.; Mebel, Alexander M.

doi:10.1039/d0cp00306a

Title: Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association

Journal Article · Mon Mar 09 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/d0cp00306a· OSTI ID:1766438

Morozov, Alexander N. ^[1];

^[1]

Florida International Univ., Miami, FL (United States)

Potential energy surface for the phenyl + propargyl radical recombination reaction has been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory for the closed-shell singlet species and at the triplet–singlet gap CASPT2/cc-pVTZ-CCSD(T)-F12/cc-pVTZ-f12//CASSCF/cc-pVTZ level of theory for the diradical species. High-pressure limit rate constants for the barrierless channels were evaluated with variable reaction coordinate transition state theory (VRC-TST). Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations have been performed to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. Here, the entrance channels of the radical association reaction produce 3-phenyl-1-propyne and phenylallene which can further dissociate/isomerize into a variety of unimolecular and bimolecular products. Theoretical evidence is presented that, at combustion relevant conditions, the phenyl + propargyl recombination provides a feasible mechanism for the addition of a second five-member ring to the first six-member aromatic ring producing the prototype two-ring species indene and indenyl. Rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-04ER15570

OSTI ID:: 1766438

Alternate ID(s):: OSTI ID: 1605038

Journal Information:: Physical Chemistry Chemical Physics. PCCP (Print), Vol. 22, Issue 13; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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