Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association
Abstract
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.
- Authors:
-
- Florida International Univ., Miami, FL (United States)
- Publication Date:
- Research Org.:
- Florida International Univ. (FIU), Miami, FL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1766438
- Alternate Identifier(s):
- OSTI ID: 1605038
- Grant/Contract Number:
- FG02-04ER15570
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP (Print)
- Additional Journal Information:
- Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 22; Journal Issue: 13; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Morozov, Alexander N., and Mebel, Alexander M. Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association. United States: N. p., 2020.
Web. doi:10.1039/d0cp00306a.
Morozov, Alexander N., & Mebel, Alexander M. Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association. United States. https://doi.org/10.1039/d0cp00306a
Morozov, Alexander N., and Mebel, Alexander M. Mon .
"Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association". United States. https://doi.org/10.1039/d0cp00306a. https://www.osti.gov/servlets/purl/1766438.
@article{osti_1766438,
title = {Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association},
author = {Morozov, Alexander N. and Mebel, Alexander M.},
abstractNote = {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.},
doi = {10.1039/d0cp00306a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 13,
volume = 22,
place = {United States},
year = {Mon Mar 09 00:00:00 EDT 2020},
month = {Mon Mar 09 00:00:00 EDT 2020}
}
Web of Science
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