Citation: ZHANG Tian-Lei, YANG Chen, FENG Xu-Kai, WANG Zhu-Qing, WANG Rui, LIU Qiu-Li, ZHANG Peng, WANG Wen-Liang. Theoretical Study on the Atmospheric Reaction of HS with HO₂: Mechanism and Rate Constants of the Major Channel[J]. Acta Physico-Chimica Sinica, ;2016, 32(3): 701-710. doi: 10.3866/PKU.WHXB201512303 shu

Theoretical Study on the Atmospheric Reaction of HS with HO₂: Mechanism and Rate Constants of the Major Channel

1.
1 Shaanxi Province Key Laboratory of Catalytic Fundamental & Application, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong 723001, Shaanxi Province, P. R. China;
2.
2 Shandong Provincial Key Laboratory of Ocean Environment Monitoring Technology, Shandong Academy of Sciences Institute of Oceanographic Instrumentation, Qingdao 266001, Shandong Province, P. R. China;
3.
3 Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China

Corresponding author: ZHANG Tian-Lei, WANG Wen-Liang,
Received Date: 20 November 2015
Available Online: 28 December 2015
Fund Project: 国家自然科学基金(21473108,21207081) (21473108,21207081)陕西理工学院科研计划项目(SLGQD13(2)-3,SLGQD13(2)-4)资助 (SLGQD13(2)-3,SLGQD13(2)-4)

The mechanism for the biradical reaction of HS with HO₂ is investigated at the CCSD(T)/6-311++ G(3df,2pd)//B3LYP/6-311+G(2df,2p) level on both the singlet and triplet potential energy surfaces, along with rate constant calculations of the major channel. The results show that there are eight reaction channels involved in the HS + HO₂ reaction system. The major channel R1 of the title reaction occurs on the triplet potential energy surfaces, and includes two pathways: Path 1 (R → ³IM1 → ³TS1 → P1(³O₂ + H₂S)) and Path 1a (R → ³IM1a → ³TS1a → P1(³O₂ + H₂S)). The rate constants k^TST, k^CVT, and k^CVT/SCT of Paths 1 and 1a for Channel R1 were evaluated using classical transition state theory (TST) and the canonical variational transition state theory (CVT), in which the small-curvature tunneling correction was included. The calculated results show that k^TST, k^CVT, and k^CVT/SCT of these two pathways decrease with rising temperature within the temperature range of 200-800 K. The variational effect was not negligible in the entire process of Path 1 and Path 1a, at the same time, the tunneling effect was considerable at lower temperature. The fitted three-parameter expressions of k^CVT/SCT for Paths 1 and 1a are k₁^CVT/SCT(200-800 K) = 1.54×10^-5T^-2.70exp(1154/T) cm³·molecule^-1·s^-1 and k_1a^CVT/SCT (200-800 K) = 5.82×10^-8T^-1.84exp(1388/T) cm³·molecule^-1·s^-1, respectively.
- HS,
- HO₂,
- Potential energy surface,
- Reaction mechanism,
- Rate constant
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Theoretical Study on the Atmospheric Reaction of HS with HO2: Mechanism and Rate Constants of the Major Channel

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Theoretical Study on the Atmospheric Reaction of HS with HO₂: Mechanism and Rate Constants of the Major Channel