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A theoretical study on gas-phase reaction of methylketene with OH: mechanism, kinetics, and insights

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Abstract

The oxidation mechanism of CH3CHCO initiated by OH is systematically studied using quantum theoretical methods. According to thermodynamic research, the dominant channel is the addition of CH3CHCO with OH generating C-IM1 (CH3CHOHCO) and C-IM2 (CH3CHCOOH), and then dissociate to the dominant products P1 (CH3CHO + CO) from C-IM1 with the lowest barrier. The rate constants for CH3CHCO + OH → C-IM1 → P1/CH3CHCO + OH → C-IM2 channels are computed through RRKM theory at 200–2000 K. The obtained overall rate constant at 298 K (7.60 × 10−11 cm3 molecule−1 s−1) is well consistent with the reported experimental value. The atmospheric lifetime of CH3CHCO is estimated to be around 1.83 h.

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Funding

This work was supported by the Natural Science Foundations of China (No. 21707062), Scientific Research Starting Foundation of Mianyang Normal University (No. QD2016A007) and by the Open Project Program of Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University (BTBU), Beijing 100048, China.

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Authors and Affiliations

  1. Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, People’s Republic of China

    Yunju Zhang, Huaming Du, Yuxi Sun, Huirong Li & Zhiguo Wang

  2. Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University (BTBU), 100048, Beijing, People’s Republic of China

    Yunju Zhang & Yongguo Liu

  3. College of Medical Technology, Chengdu University of Traditional Chinese Medicine Liutai Avenue, Wenjiang District, ChengDu, People’s Republic of China

    Meilian Zhao

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  1. Yunju Zhang
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  2. Yongguo Liu
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Contributions

Yongguo Liu, Huaming Du, Meilian Zhao, Yuxi Sun, Huirong Li Zhiguo Wang: calculation, data curation, formal analysis, investigation. Yunju Zhang: calculation, writing-review and editing.

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Correspondence to Yunju Zhang.

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Zhang, Y., Liu, Y., Du, H. et al. A theoretical study on gas-phase reaction of methylketene with OH: mechanism, kinetics, and insights. Struct Chem 33, 49–56 (2022). https://doi.org/10.1007/s11224-021-01811-0

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