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Title: Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited

Abstract

Quantum chemical calculations of the C6H5O2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O(3P) and phenyl + O2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multi-reference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O(3P) reaction. Stationary points on the C6H5O2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multi-reference character of the wave function. Conventional, variational, and variable reaction coordinate transition state theories were employed in Rice-Ramsperger-Kassel-Marcus Master Equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. Here, the main bimolecular product channels of the phenoxy + O(3P) reaction are concluded to be para/ortho-benzoquinone + H, 2,4-cyclopentadienone + HCO, and, at high temperatures, also phenyl + O2. The main bimolecular product channels of the phenyl + O2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures, and phenoxy + O(3P) at higher temperatures. Both for the phenoxy + O(3P) and phenyl + O2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular productmore » channels.« less

Authors:
 [1];  [2];  [2]; ORCiD logo [1]
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  1. Florida International Univ. (FIU), Miami, FL (United States)
  2. Samara National Research Univ. (Russia); Lebedev Physical Inst., Samara (Russia)
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:
1843950
Grant/Contract Number:  
FG02-04ER15570
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 125; Journal Issue: 18; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Energy; Kinetic parameters; Chemical calculations; Phenyls; Molecules

Citation Formats

Morozov, Alexander N., Medvedkov, Iakov A., Azyazov, Valeriy N., and Mebel, Alexander M. Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited. United States: N. p., 2021. Web. doi:10.1021/acs.jpca.1c01545.
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Morozov, Alexander N., Medvedkov, Iakov A., Azyazov, Valeriy N., & Mebel, Alexander M. Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited. United States. https://doi.org/10.1021/acs.jpca.1c01545
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Morozov, Alexander N., Medvedkov, Iakov A., Azyazov, Valeriy N., and Mebel, Alexander M. Fri . "Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited". United States. https://doi.org/10.1021/acs.jpca.1c01545. https://www.osti.gov/servlets/purl/1843950.
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@article{osti_1843950,
title = {Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited},
author = {Morozov, Alexander N. and Medvedkov, Iakov A. and Azyazov, Valeriy N. and Mebel, Alexander M.},
abstractNote = {Quantum chemical calculations of the C6H5O2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O(3P) and phenyl + O2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multi-reference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O(3P) reaction. Stationary points on the C6H5O2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multi-reference character of the wave function. Conventional, variational, and variable reaction coordinate transition state theories were employed in Rice-Ramsperger-Kassel-Marcus Master Equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. Here, the main bimolecular product channels of the phenoxy + O(3P) reaction are concluded to be para/ortho-benzoquinone + H, 2,4-cyclopentadienone + HCO, and, at high temperatures, also phenyl + O2. The main bimolecular product channels of the phenyl + O2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures, and phenoxy + O(3P) at higher temperatures. Both for the phenoxy + O(3P) and phenyl + O2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular product channels.},
doi = {10.1021/acs.jpca.1c01545},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 18,
volume = 125,
place = {United States},
year = {Fri Apr 30 00:00:00 EDT 2021},
month = {Fri Apr 30 00:00:00 EDT 2021}
}
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