High-level theoretical study of the hydrogen abstraction reaction H2S + O2 = SH + HO2 and prediction of the rate constants

Wang, Quan‐De; Sun, Mao-Mao; Liang, Jinhu

doi:10.1016/j.comptc.2019.03.023

Cited by 4 publications

(2 citation statements)

References 34 publications

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“…Generally, a single-reference coupled cluster calculation for closed-shell species is considered to be reliable if the T 1 diagnostic value is within 0.020. For open-shell systems, a higher threshold value for the T 1 diagnostic up to 0.044 can be acceptable. , For all the species during open-shell CCSD(T) calculations, it is found that all T 1 diagnostics values are within 0.030 except for the TSs of allene and 1,3-butene, the values of which are close to 0.039. Thus, the employed single-reference methods are adequate in this work.…”

Section: Computational Methodologymentioning

confidence: 87%

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H₂/C₁–C₄ Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

Liang

Cao

et al. 2022

ACS Omega

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The hydrogen atom abstraction by the methyl peroxy radical (CH 3 O 2 ) is an important reaction class in detailed chemical kinetic modeling of the autoignition properties of hydrocarbon fuels. Systematic theoretical studies are performed on this reaction class for H 2 /C 1 −C 4 fuels, which is critical in the development of a base model for large fuels. The molecules include hydrogen, alkanes, alkenes, and alkynes with a carbon number from 1 to 4. The B2PLYP-D3/cc-pVTZ level of theory is employed to optimize the geometries of all of the reactants, transition states, and products and also the treatments of hindered rotation for lower frequency modes. Accurate benchmark calculations for abstraction reactions of hydrogen, methane, and ethylene with CH 3 O 2 are performed by using the coupled cluster method with explicit inclusion of single and double electron excitations and perturbative inclusion of triple electron excitations (CCSD(T)), the domain-based local pair-natural orbital coupled cluster method (DLPNO-CCSD(T)), and the explicitly correlated CCSD(T)-F12 method with large basis sets. Reaction rate constants are computed via conventional transition state theory with quantum tunneling corrections. The computed rate constants are compared with literature values and those employed in detailed chemical kinetic mechanisms. The calculated rate constants are implemented into the recently developed NUIGMECH1.1 base model for kinetic modeling of ignition properties.

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Section: Computational Methodologymentioning

confidence: 87%

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H₂/C₁–C₄ Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

Liang

Cao

et al. 2022

ACS Omega

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“…For closed-shell systems, a T1 diagnostic value below 0.02 is generally considered acceptable [40]. In open-shell systems, this threshold is higher, around 0.045 [41], as seen in species like oxygencontaining compounds and radicals [42].…”

Section: Calculation Methodsmentioning

confidence: 99%

A theoretical study on toluene oxidization by OH radical

Mao,

Yang,

Liu

et al. 2024

BMC Chemistry

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Toluene, a prominent member of volatile organic compounds (VOCs), exerts a substantial adverse influence on both human life and the environment. In the context of advanced oxidation processes, the ·OH radical emerges as a highly efficient oxidant, pivotal in the elimination of VOCs. This study employs computational quantum chemistry methods (G4MP2//B3LYP/6-311++G(d,p)) to systematically investigate the degradation of toluene by ·OH radicals in an implicit solvent model, and validates the rationale of choosing a single-reference method using T1 diagnostics. Our results suggest three possible reaction mechanisms for the oxidation of toluene by ·OH: firstly, the phenyl ring undergoes a hydrogen abstraction reaction followed by direct combination with ·OH to form cresol; secondly, ·OH directly adds to the phenyl ring, leading to ring opening; thirdly, oxidation of sidechain to benzoic acid followed by further addition and ring opening. The last two oxidation pathways involve the ring opening of toluene via the addition of ·OH, significantly facilitating the process. Therefore, both pathways are considered feasible for the degradation of toluene. Subsequently, the UV-H2O2 system was designed to induce the formation of ·OH for toluene degradation and to identify the optimal reaction conditions. It was demonstrated that ·OH and 1O2 are the primary active species for degrading toluene, with their contribution ranking as ·OH > 1O2. The intermediates in the mixture solution after reactions were characterized using GC–MS, demonstrating the validity of theoretical predictions. A comparative study of the toluene consumption rate revealed an experimental comprehensive activation energy of 10.33 kJ/mol, which is consistent with the preliminary activation energies obtained via theoretical analysis of these three mechanisms (0.56 kJ/mol to 13.66 kJ/mol), indicating that this theoretical method can provide a theoretical basis for experimental studies on the oxidation of toluene by ·OH.

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Theoretical study of the hydrogen abstraction reactions from substituted phenolic species

Wang

Sun

Liang

2021

Computational and Theoretical Chemistry

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High-level theoretical study of the hydrogen abstraction reaction H2S + O2 = SH + HO2 and prediction of the rate constants

Cited by 4 publications

References 34 publications

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H₂/C₁–C₄ Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H₂/C₁–C₄ Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

A theoretical study on toluene oxidization by OH radical

Theoretical study of the hydrogen abstraction reactions from substituted phenolic species

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High-level theoretical study of the hydrogen abstraction reaction H2S + O2 = SH + HO2 and prediction of the rate constants

Cited by 4 publications

References 34 publications

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H2/C1–C4 Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H2/C1–C4 Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

A theoretical study on toluene oxidization by OH radical

Theoretical study of the hydrogen abstraction reactions from substituted phenolic species

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High-level theoretical study of the hydrogen abstraction reaction H2S + O2 = SH + HO2 and prediction of the rate constants

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H₂/C₁–C₄ Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H₂/C₁–C₄ Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling