Theoretical Investigation of Rate Rules for H-Intermigration Reactions for Cyclic Alkylperoxy Radicals

As a starting channel, the H-intermigration reaction of alkylperoxy radicals (ROO radicals) that yields hydroperoxyl alkyl radicals (QOOH radicals) determines the low-temperature chemistry of alkanes. In this work, this type of reaction was investigated for typical cyclic alkanes, which are importan...

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Bibliographic Details
Published in:Energies (Basel) 2023-03, Vol.16 (6), p.2881
Main Authors: Yang, Kun, Tian, Zemin, Li, Jinghua, Yan, Yingwen
Format: Article
Language:English
Subjects:
ab initio calculation
Alkanes
Analysis
Biodiesel fuels
Biofuels
Channels
Chemistry
cycloalkylperoxy radicals
Decomposition
Density functional theory
Density functionals
Energy
H-intermigration reaction
Hydrocarbons
Investigations
Low temperature
Methods
Oxidation
Pressure dependence
Radicals
rate rules
Rotors
Vibrational spectra
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Summary:As a starting channel, the H-intermigration reaction of alkylperoxy radicals (ROO radicals) that yields hydroperoxyl alkyl radicals (QOOH radicals) determines the low-temperature chemistry of alkanes. In this work, this type of reaction was investigated for typical cyclic alkanes, which are important fuel components and soot precursors, using theoretical ab initio methods. First, all the molecular geometries and vibrational frequencies were computed using the density functional theory method and the single point energies were refined using the post-Hartree fork method (M062X/6-311G(d,p)//DLPNO-CCSD(T)/CBS). Then, high-pressure limit rate constants were evaluated with tight transition state theory, with which tunneling effects were considered using the Eckart model and low-frequency torsion modes were modeled as hindered rotors. Pressure-dependent rate constants were also calculated for typical reaction channels. Rate expressions in the Arrhenius form for 91 reactions are proposed. All reactions were categorized into seven reaction types and the rate rule for each reaction type was estimated with uncertainty factors of three to six. These rules can be potentially used in the development of low-temperature kinetic mechanisms for cycloalkanes. A comparison between different reaction types was also performed and the favorable channels are discussed.
ISSN:1996-1073
1996-1073
DOI:10.3390/en16062881