Theoretical investigations on mechanisms and kinetics of methylketene with O(3P) reaction in the atmosphere

Yunju Zhang; Yongguo Liu; Meilian Zhao; Huaming Du; Yuxi Sun; Huirong Li; Zhiguo Wang

doi:10.1007/s00894-021-04850-w

Theoretical investigations on mechanisms and kinetics of methylketene with O(³P) reaction in the atmosphere

J Mol Model. 2021 Jul 21;27(8):228. doi: 10.1007/s00894-021-04850-w.

Authors

Yunju Zhang^{1

2}, Yongguo Liu³, Meilian Zhao⁴, Huaming Du⁵, Yuxi Sun⁵, Huirong Li⁵, Zhiguo Wang⁵

Affiliations

¹ Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, People's Republic of China. zhangyj010@nenu.edu.cn.
² Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University (BTBU), 100048, Beijing, People's Republic of China. zhangyj010@nenu.edu.cn.
³ Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University (BTBU), 100048, Beijing, People's Republic of China.
⁴ College of Medical Technology, Chengdu University of Traditional Chinese Medicine Liutai Avenue, Wenjiang District, Chengdu, People's Republic of China.
⁵ Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, People's Republic of China.

PMID: 34291349
DOI: 10.1007/s00894-021-04850-w

Abstract

The O(³P)-initiated conversion mechanism and dynamics of CH₃CHCO were researched in atmosphere by executing density functional theory (DFT) computations. Optimizations of all the species and single-point energy computations were implemented at the B3LYP/6-311++G(d,p) and CCSD(T)/cc-pVTZ level, respectively. The explicit oxidation mechanism was introduced and discussed. The results state clearly that the O(³P) association was more energetically beneficial than the abstraction of H. The rate coefficients over the probable temperature range of 200-3000 K were forecasted by implementing Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Specifically, the total rate coefficient of O(³P) association reactions is 1.19 × 10^-11 cm³ molecule^-1 s^-1 at 298 K, which is consistent with the experimental results (1.16 × 10^-11 cm³ molecule^-1 s^-1). The rate coefficients for the O(³P) with CH₂CO, CH₃CHCO, and (CH₃)₂CCO suggest that rate coefficient of ketene derivatives increase with the increase of methylation degree. Graphical abstract.

Keywords: Methylketene; O(3P); Rate constants; Reaction mechanism.

Abstract

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