Acta Phys. -Chim. Sin. ›› 2016, Vol. 32 ›› Issue (3): 701-710.doi: 10.3866/PKU.WHXB201512303

• ARTICLE • Previous Articles     Next Articles

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

Tian-Lei ZHANG1,*(),Chen YANG1,Xu-Kai FENG1,Zhu-Qing WANG2,Rui WANG1,Qiu-Li LIU1,Peng ZHANG1,Wen-Liang WANG3,*()   

  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 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 Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P.R.China
  • Received:2015-11-20 Published:2016-03-04
  • Contact: Tian-Lei ZHANG,Wen-Liang WANG;
  • Supported by:
    the National Natural Science Foundation of China(21473108, 21207081);Funds of Research Programs of ShaanxiUniversity of Technology, China(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 kTST, kCVT, and kCVT/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 kTST, kCVT, and kCVT/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 kCVT/SCT for Paths 1 and 1a are k1CVT/SCT(200-800 K) = 1.54×10-5T-2.70exp(1154/T) cm3·molecule-1·s-1 and k1aCVT/SCT (200-800 K) = 5.82×10-8T-1.84exp(1388/T) cm3·molecule-1·s-1, respectively.

Key words: HS, HO2, Potential energy surface, Reaction mechanism, Rate constant