Citation: Lyu Longmei, Geng Lin, Wen Mingjie, Qiao Zhangyu, Kou Weihua, Wang Yan, Tian Shaobo, Wang Rui. Study on the Atmospheric Reaction of NO₂ with HSO:Mechanism and Kinetics[J]. Chemistry, ;2019, 82(6): 534-541, 503. shu

Study on the Atmospheric Reaction of NO₂ with HSO:Mechanism and Kinetics

Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong 723000

Corresponding author: Wang Rui, wangrui830413@163.com
Received Date: 16 October 2018
Accepted Date: 30 March 2019

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The mechanism for the reaction between NO₂ and HSO was investigated at the CCSD(T)/aug-cc-pVTZ //B3LYP/aug-cc-pVTZ level on both the singlet and triplet potential energy surfaces (PESs). The results showed that there are three hydrogen abstraction reaction channels on both singlet [R1 HN(O)O+¹SO), R2 (cis-HONO+¹SO), and R3 (trans-HONO+¹SO)] and triplet [R6 (HN(O)O+³SO), R7(cis-HONO+³SO), and R8(trans-HONO+³SO)] PESs, as well as two oxygen abstraction reaction channels on both singlet [R4 (NO+HS(O)O)and R5(H+SO₂+NO)] and triplet [R9(HS(O)O+NO) and R10 (H+SO₂+NO)] on the triplet PESs. Among these channels, Channel R2 (cis-HONO+¹SO) on the singlet PESs is the favorable channel. The rate constants of above reaction channels were evaluated using classical transition state theory (TST) and Wigner correction. The calculated results showed that the reaction channel of cis-HONO+SO formations is favorable and its rate constant, at 298K, is 7.78×10^-13cm³·molecule^-1·s^-1, which is in good agreement with experimental value (9.6×10^-12cm³·molecule^-1·s^-1). Water molecule catalyzed R2 (cis-HONO+¹SO) occurs through two different channels of NO₂+H₂O…HSO and NO₂+H₂O…HSO (HSO+NO₂…H₂O), where the barriers of the two channels respectively are enhanced by 49.97 kcal·mol^-1 and 20.67 kcal·mol^-1 than that of the naked reaction of R2, indicating that the effect of water molecules on the NO₂+HSO reaction can be neglected in the actual atmospheric environment.
- NO₂,
- HSO,
- Singlet and triplet PES,
- Reaction mechanism,
- Rate constant
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Study on the Atmospheric Reaction of NO₂ with HSO:Mechanism and Kinetics