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
1. [1]
  (1) Farquhar, J.; Bao, H.; Thiemens, M. Science 2000, 289 (5184), 756. doi: 10.1126/science.289.5480.756
2. [2]
  (2) Martínez, E.; Albaladejo, J.; Notario, A.; Jiménez, E. Atmos. Environ. 2000, 34 (29), 5295. doi: 10.1016/S1352-2310(00)00348-4
3. [3]
  (3) Vandeputte, A. G.; Reyniers, M. F.; Marin, G. B. J. Phys. Chem. A 2010, 114 (39), 10531. doi: 10.1021/jp103357z
4. [4]
  (4) Williams, M. B.; Campuzano-Jost, P.; Hynes, A. J.; Pounds, A.J. J. Phys. Chem. A 2009, 113 (24), 6697. doi: 10.1021/jp9010668
5. [5]
  (5) Wang, W.; Xin, J.; Zhang, Y.; Wang, W.; Lu, Y. Int. J. Quantum Chem. 2011, 111 (3), 644. doi: 10.1002/qua.22446
6. [6]
  (6) Yan, J.; Yang, J.; Liu, Z. Environ. Sci. Technol. 2005, 39 (13), 5043. doi: 10.1021/es048398c
7. [7]
  (7) Resende, S. M.; Ornellas, F. R. J. Phys. Chem. A 2000, 104(51), 11934. doi: 10.1021/jp001751q
8. [8]
  (8) Black, G. J. Chem. Phys. 1984, 80 (3), 1103. doi: 10.1063/1.446838
9. [9]
  (9) Atkinson, R.; Baulch, D. L.; Cox, R. A.; Crowley, J. N.; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; Rossi, M. J.; Troe, J. Atmos. Chem. Phys. 2004, 4 (6), 1461. doi: 10.5194/acp-4-1461-2004
10. [10]
  (10) Herndon, S. C.; Froyd, K. D.; Lovejoy, E. R.; Ravishankara, A.R. J. Phys. Chem. A 1999, 103 (34), 6778. doi: 10.1021/jp9911853
11. [11]
  (11) Friedl, R. R.; Brune, W. H.; Anderson, J. G. J. Phys. Chem.1985, 89 (25), 5505. doi: 10.1021/j100271a038
12. [12]
  (12) Nesbitt, D. J.; Leone, S. R. J. Chem. Phys. 1980, 72 (3), 1722. doi: 10.1063/1.439284
13. [13]
  (13) Domagal-Goldman, S. D.; Meadows, V. S.; Claire, M.W.Astrobiology 2011, 11 (5), 419. doi: 10.1089/ast.2010.0509
14. [14]
  (14) Shum, L. G. S.; Benson, S.W. Int. J. Chem. Kinet. 1985, 17(7), 749. doi: 10.1002/kin. 550170705
15. [15]
  (15) Imai, N.; Toyama, O. Bull. Chem. Soc. Jpn. 1961, 34 (3), 328. doi: 10.1246/bcsj.34.328
16. [16]
  (16) Amphlett, J. C.; Whittle, E. Trans. Faraday Soc. 1967, 63, 2695. doi: 10.1039/TF9676302695
17. [17]
  (17) Perner, V. D.; Franken, T. Ber. Bunsenges. Phys. Chem. 1969, 73 (8-9), 897. doi: 10.1002/bbpc. 19690730830
18. [18]
  (18) Long, B.; Zhang, W. J.; Tan, X. F.; Long, Z.W.; Wang, Y. B.; Ren, D. S. J. Phys. Chem. A 2011, 115 (8), 1350. doi: 10.1021/jp107550w
19. [19]
  (19) Allodi, M. A.; Dunn, M. E.; Livada, J.; Kirschner, K. N.; Shields, G. C. J. Phys. Chem. A 2006, 110 (49), 13283. doi: 10.1021/jp064468l
20. [20]
  (20) Zhou, Y. Z.; Zhang, S.W.; Li, Q. S. Chem. J. Chin. Univ. 2006, 27 (8), 1496. [周玉芝, 张绍文, 李前树. 高等学校化学学报, 2006, 27 (8), 1496.]
21. [21]
  (21) Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90 (4), 2154. doi: 10.1063/1.456010
22. [22]
  (22) Lee, Y. S.; Kucharski, S. A.; Bartlett, R. J. J. Chem. Phys.1984, 81 (12), 5906. doi: 10.1063/1.447591
23. [23]
  (23) Liu, Z. R.; Xu, B. E.; Zeng, Y. L.; Li, X. Y.; Meng, L. P.; Sun, Z.; Zhang, X. Y.; Zhang, P. Acta Chim. Sin. 2011, 69 (17), 1957. [刘占荣, 许保恩, 曾艳丽, 李晓艳, 孟令鹏, 孙政, 张雪英, 张萍. 化学学报, 2011, 69 (17), 1957.]
24. [24]
  (24) Xu, Q.; Wang, R.; Zhang, T. L.; Zhang, H. L.; Wang, Z. Y.; Wang, Z. Q. Chem. J. Chin. Univ. 2014, 35 (10), 2191. [许琼, 王睿, 张田雷, 张浩林, 王志银, 王竹青. 高等学校化学学报, 2014, 35 (10), 2191.] doi: 10.7503/cjcu20140310
25. [25]
  (25) Frisch, M. J.; Trucks, G.W.; Pople, J. A.; et al. Gaussian 09, Revision A.01; Gaussian Inc.: Pittsburgh, PA, 2009.
26. [26]
  (26) Zhang, S.W.; Truong, N. T. VKLab, version 1.0; University ofUtah, Salt Lake City, USA, 2001.
27. [27]
  (27) Garrett, B. C.; Truhlar, D. G.; Grev, R. S.; Magnuson, A.W.J. Phys. Chem. 1980, 84 (13), 1730. doi: 10.1021/j100450a013
28. [28]
  (28) Liu, Y. P.; Lynch, G. C.; Truong, T. N.; Lu, D. H.; Truhlar, D.G.; Garrett, B. C. J. Am. Chem. Soc. 1993, 115 (6), 2408. doi: 10.1021/ja00059a041
29. [29]
  (29) Anglada, J. M.; Domingo, V. M. J. Phys. Chem. A 2005, 109(47), 10786. doi: 10.1021/ jp054018d
30. [30]
  (30) Si, W. J.; Zhuo, S. P.; Ju, G. Z. Acta Phys. -Chim. Sin. 2003, 19(10), 974. [司维江, 禚淑萍, 居冠之. 物理化学学报, 2003, 19(10), 974.] doi: 10.3866/PKU.WHXB20031019
31. [31]
  (31) From the NIST chemistry webbook, http://webbook.nist.gov/chemistry.
32. [32]
  (32) Gonzalez, C.; Theisen, J.; Zhu, L.; Schlegel, H. B.; Hase, W.L.; Kaiser, E.W. J. Phys. Chem. 1991, 95 (18), 6784. doi: 10.1021/j100171a010
33. [33]
  (33) Gonzalez, C.; Theisen, J.; Schlegel, H. B.; HaseW. L.; Kaiser, E.W. J. Phys. Chem. 1992, 96 (4), 1767. doi: 10.1021/j100183a051
34. [34]
  (34) Zhang, T. L.; Wang, W. L.; Li, C. Y.; Du, Y. M.; Lv, J. RSC Adv. 2013, 3 (20), 7381. doi: 10.1039/c3ra40341f
35. [35]
  (35) Hammond, G. S. J. Am. Chem. Soc. 1955, 77 (2), 334. doi: 10.1021/ja01607a027
36. [36]
  (36) Lu, Y. X.; Wang, W. L.; Wang, W. N.; Liu, Y. Y.; Zhang, Y.Acta Chim. Sin. 2010, 68 (13), 1253. [卢彦霞, 王文亮, 王渭娜, 刘英英, 张越. 化学学报, 2010, 68 (13), 1253.]
37. [37]
  (37) Liu, Y.; Wang, W.; Zhang, T.; Cao, J.; Wang, W.; Zhang, Y.Comput. Theor. Chem. 2011, 964 (1), 169. doi: 10.1016/j.comptc.2010.12.017
38. [38]
  (38) Zhang, Y.; Zhang, W.; Zhang, T.; Tian, W.; Wang, W. Comput. Theor. Chem. 2012, 994, 65. doi: 10.1016/j.comptc.2012.06.016
1. [1]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
2. [2]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
3. [3]
  Jia Zhou . Constructing Potential Energy Surface of Water Molecule by Quantum Chemistry and Machine Learning: Introduction to a Comprehensive Computational Chemistry Experiment. University Chemistry, 2024, 39(3): 351-358. doi: 10.3866/PKU.DXHX202309060
4. [4]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
5. [5]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
6. [6]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
7. [7]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
8. [8]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
9. [9]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
10. [10]
  Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
11. [11]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
12. [12]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
13. [13]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
14. [14]
  Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
15. [15]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
16. [16]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
17. [17]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
18. [18]
  Yuejiao An , Wenxuan Liu , Yanfeng Zhang , Jianjun Zhang , Zhansheng Lu . Revealing Photoinduced Charge Transfer Mechanism of SnO₂/BiOBr S-Scheme Heterostructure for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2407021-. doi: 10.3866/PKU.WHXB202407021
19. [19]
  Xuanzhu Huo , Yixi Liu , Qiyu Wu , Zhiqiang Dong , Chanzi Ruan , Yanping Ren . Integrated Experiment of “Electrolytic Preparation of Cu₂O and Gasometric Determination of Avogadro’s Constant: Implementation, Results, and Discussion: A Micro-Experiment Recommended for Freshmen in Higher Education at Various Levels Across the Nation. University Chemistry, 2024, 39(3): 302-307. doi: 10.3866/PKU.DXHX202308095
20. [20]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(571)
HTML views(35)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

Metrics

通讯作者: 陈斌, bchen63@163.com

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