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

Kun Yang, Zemin Tian (), Jinghua Li and Yingwen Yan
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Kun Yang: College of Energy and Power Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
Zemin Tian: College of Energy and Power Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
Jinghua Li: College of Energy and Power Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
Yingwen Yan: College of Energy and Power Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China

Energies, 2023, vol. 16, issue 6, 1-20

Abstract: 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.

Keywords: cycloalkylperoxy radicals; rate rules; H-intermigration reaction; ab initio calculation (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2023
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