一种量子化学组合方法及其应用于汞对硫酸气溶胶形成影响的研究

doi:10.6023/A21040147

摘要/Abstract

本工作建立了一种量子化学的组合方法并应用于研究在硫和汞复合污染地区, 汞及其化合物是否会参与和驱动硫酸气溶胶形成. 该方法采用Molclus Genmer模块生成数以百万计的巨量团簇初始结构, 用自洽紧束缚GFN2-xTB方法预优化, 再用B3PW91-D3(BJ) DFT方法重新优化, 结合能经ωB97M-D3(BJ)校正后计算出团簇的热力学函数, 以其生成过程Gibbs自由能变大小排序, 获得团簇稳定序列及其对应的结合能和热力学函数. 然后用该方法研究了汞及其化合物、硫酸和水生成的8种团簇模型共计240万个结构, 结果表明HgSO₄, HgO等汞的极性化合物以及Hg₂²⁺和 Hg²⁺能够促进硫酸气溶胶的形成, 而Hg以及无极性的HgCl₂和Hg₂Cl₂对硫酸气溶胶成核的影响较小. 这一结论对硫、汞复合污染环境下, 硫酸气溶胶成核机制探讨提供了有价值的预测.

关键词: 量子化学, 组合方法, 硫酸气溶胶, 汞, 热力学函数

Haze weather has been occurring frequently in recent years, and studies have shown that its formation mechanism is related to the nucleation of sulfuric acid aerosols. How mercury and its compounds affect the formation and growth of sulfuric acid aerosols is completely unclear in polluted areas where sulfur and mercury coexist. In order to explore this problem theoretically, we established a new quantum chemistry combination method. Millions of cluster structures are generated by using the Molclus Genmer module. The cluster geometries are preliminarily optimized by the GFN2-xTB method and sorted according to the Gibbs free energy changes of the cluster generation process. The top 100 optimized structures were re-optimized using the B3PW91-D3(BJ) method. In order to accurately calculate the binding energy of clusters, we established a small benchmark set based on the composition and structural characteristics of the clusters studied in the project, and used the CCSD(T)/CBS method to calculate the binding energy of each cluster model in the benchmark set. Using the binding energy as a standard, the best method selected from 42 DFT methods is ωB97M-D3(BJ). The binding energy calculated by B3PW91-D3(BJ) is corrected by the results of the ωB97M-D3(BJ) method to obtain an accurate thermodynamic function value. It is worth mentioning that the combined method was used to study a total of 2.4 million structures in 8 cluster models formed by mercury and its typical compounds, sulfuric acid and water. The results show that polar compounds of mercury such as HgSO₄ and HgO, together with Hg₂²⁺ and Hg²⁺, can promote sulfuric acid aerosol formation, while Hg and non-polar HgCl₂ and Hg₂Cl₂ have almost no effect on the nucleation of sulfuric acid aerosol. In addition, we found that the conclusion holds true for the temperature interval of the troposphere at standard atmospheric pressure. This conclusion provides valuable predictions for the studies on sulfuric acid aerosol nucleation mechanisms under the combined sulfur and mercury pollution environment.

Key words: quantum chemistry, combination method, sulfuric acid aerosols, mercury, thermodynamic function

引用此文

李程桥, 王一波. 一种量子化学组合方法及其应用于汞对硫酸气溶胶形成影响的研究[J]. 化学学报, 2021, 79(8): 1065-1072.

Chengqiao Li, Yibo Wang. A Combination Method of Quantum Chemistry and Its Application to the Study of the Effects of Mercury on the Formation of Sulfuric Acid Aerosol[J]. Acta Chimica Sinica, 2021, 79(8): 1065-1072.

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图/表 6

图1. DFT/def2-QZVPP计算测试集的RMSD和MAX比较, MAX取绝对值

Figure 1. Comparison of RMSD and MAX of DFT/def2-QZVPP calculation benchmark set, MAX takes the absolute value

图2. 组合方法的计算流程示意图

Figure 2. Schematic representation of the calculation process of the combined method ΔG' represent Δ G bind B 3 PW 91 - D 3 BJ, ΔE' represent Δ E bind B 3 PW 91 - D 3 BJ, ΔE represent Δ E bind ωB 97 M - D 3 BJ

图3. B3PW91-D3(BJ)/def2-SV(P)方法计算8种团簇生成过程的Gibbs自由能变最大结构

Figure 3. The Gibbs free energy change maximum structure of the 8 cluster formation processes calculated at the B3PW91-D3(BJ)/def2-SV(P) level of theory

No.	Reaction	ΔE		ΔH		ΔS		ΔG
No.	Reaction	average	max	average	max	average	max	average	max
1	H₂SO₄+30H₂O=>(H₂SO₄)(H₂O)₃₀	–1391.81	–1426.16	–2367.10	–2388.31	–4.52	–4.56	–809.65	–816.38
2	Hg+H₂SO₄+30H₂O=>(Hg)(H₂SO₄)(H₂O)₃₀	–1417.62	–1430.68	–2397.68	–2434.67	–4.60	–4.64	–791.74	–799.19
3	Hg₂Cl₂+H₂SO₄+30H₂O=>(Hg₂Cl₂)(H₂SO₄)(H₂O)₃₀	–1429.97	–1468.29	–2512.99	–2550.94	–4.64	–4.69	–749.61	–782.03
4	HgSO₄+H₂SO₄+30H₂O=>(HgSO₄)(H₂SO₄)(H₂O)₃₀	–1885.06	–1896.52	–2857.13	–2888.97	–4.73	–4.77	–1291.35	–1297.54
5	HgO+H₂SO₄+30H₂O=>(HgO)(H₂SO₄)(H₂O)₃₀	–1802.43	–1826.57	–2787.05	–2833.99	–4.69	–4.73	–1177.92	–1186.08
6	HgCl₂+H₂SO₄+30H₂O=>(HgCl₂)(H₂SO₄)(H₂O)₃₀	–1411.97	–1420.72	–2461.15	–2486.97	–4.64	–4.69	–766.89	–774.04
7	Hg₂²⁺+H₂SO₄+30H₂O=>(Hg₂²⁺)(H₂SO₄)(H₂O)₃₀	–2271.91	–2295.89	–3413.64	–3456.49	–4.69	–4.73	–1695.44	–1700.54
8	Hg²⁺+H₂SO₄+30H₂O=>(Hg²⁺)(H₂SO₄)(H₂O)₃₀	–2715.04	–2749.18	–3818.61	–3849.03	–4.60	–4.69	–2051.08	–2069.20

表1. 8种团簇生成过程的结合能和热力学函数(单位: kJ/mol)

Table 1. Binding energies and thermodynamic functions of 8 cluster formation processes (unit: kJ/mol)

图4. 8种团簇生成过程的ΔG随温度变化关系

Figure 4. The relationship between ΔG and temperature of 8 cluster formation processes

图5. 2019年01月~2020年10月A地与B地(a), C地与D地(b)大气中PM10和PM2.5浓度变化

Figure 5. Changes in atmospheric PM10 and PM2.5 concentrations in A and B place (a), C and D place (b) from January 2019 to October 2020

参考文献 38

[1]	Sipilä, M.; Berndt, T.; Petäjä, T.; Brus, D.; Vanhanen, J.; Stratmann, F.; Patokoski, J.; Mauldin, R. L.; Hyvärinen, A. P.; Lihavainen, H.; Kulmala, M. Science 2010, 327, 1243. doi: 10.1126/science.1180315 pmid: 20203046
[2]	Asaduzzaman, A.; Riccardi, D.; Afaneh, A. T.; Cooper, S. J.; Smith, J. C.; Wang, F.; Parks, J. M.; Schreckenbach, G. Acc. Chem. Res. 2019, 52, 379. doi: 10.1021/acs.accounts.8b00454
[3]	Hong, Q.; Xie, Z.; Liu, C.; Wang, F.; Xie, P.; Kang, H.; Xu, J.; Wang, J.; Wu, F.; He, P.; Mou, F.; Fan, S.; Dong, Y.; Zhan, H.; Yu, X.; Chi, X.; Liu, J. Atmos. Chem. Phys. 2016, 16, 13807. doi: 10.5194/acp-16-13807-2016
[4]	Li, L.; Zhang, Y. Y.; Jiao, C. Y.; Yao, Y. W.; Zhang, H.; Tian, Y. M. Environ. Monit. China 2019, 35, 40 (in Chinese.)
	李亮, 张艳艳, 焦聪颖, 姚雅伟, 张辉, 田英明, 中国环境监测, 2019, 35, 40.)
[5]	Doyle, G. J. J. Chem. Phys. 1961, 35, 795. doi: 10.1063/1.1701218
[6]	Jaecker, V. A.; Mirabel, P. Atmos. Environ. 1989, 23, 2053. doi: 10.1016/0004-6981(89)90530-1
[7]	Sucarrat, M. T.; Francisco, J. S.; Anglada, J. M. J. Am. Chem. Soc. 2012, 134, 20632. doi: 10.1021/ja307523b
[8]	Kildgaard, J. V.; Mikkelsen, K. V.; Bilde, M.; Elm, J. J. Phys. Chem. A 2018, 122, 5026. doi: 10.1021/acs.jpca.8b02758 pmid: 29741906
[9]	Humphries, R. S.; Schofield, R.; Keywood, M. D.; Ward, J.; Pierce, J. R.; Gionfriddo, C. M.; Tate, M. T.; Krabbenhoft, D. P.; Galbally, I. E.; Molloy, S. B.; Klekociuk, A. R.; Johnston, P. V.; Kreher, K.; Thomas, A. J.; Robinson, A. D.; Harris, N. R.P.; Johnson, R.; Wilson, S. R. Atmos. Chem. Phys. 2015, 15,13339.
[10]	Lu, T. Molclus program, Version 1.8.7, Beijing Kein Research Center for Natural Science, China, 2018, http://www.keinsci.com/research/molclus.html
[11]	Bannwarth, C.; Ehlert, S.; Grimme, S. J. Chem. Theory Comput. 2019, 15, 1652. doi: 10.1021/acs.jctc.8b01176
[12]	Tsuzuki, S.; Honda, K.; Uchimaru, T.; Mikami, M.; Tanabe, K. J. Am. Chem. Soc. 2002, 124, 104. pmid: 11772067
[13]	Hu, M.; Shang, D. J.; Guo, S.; Wu, Z. J. Acta Chim. Sinica 2016, 74, 385 (in Chinese.) doi: 10.6023/A16020105
	胡敏, 尚冬杰, 郭松, 吴志军, 化学学报, 2016, 74, 385.) doi: 10.6023/A16020105
[14]	Elm, J.; Passananti, M.; Kurtén, T.; Vehkamäki, H. J. Phys. Chem. A 2017, 121, 6155. doi: 10.1021/acs.jpca.7b05658
[15]	Yang, P.; Ye, Z. L.; Jiang, G. Y.; Li, Z.; Ding, C. F.; Hou, H. Q. Acta Chim. Sinica 2009, 67, 2031 (in Chinese.)
	杨鹏, 叶招莲, 蒋公羽, 李周, 丁传凡, 侯惠奇, 化学学报, 2009, 67, 2031.)
[16]	Lu, Q.; Luo, Q.; Huang, S.; Li, Y.; Wan, J. J. Chem. Phys. A 2016, 120, 4560. doi: 10.1021/acs.jpca.6b05529
[17]	Lu, Q.; Luo, Q.; Huang, S.; Li, Y. Phys. Chem. Chem. Phys. 2017, 19, 28434. doi: 10.1039/C7CP05610A
[18]	Rasmussen, F. R.; Besel, V.; Mikkelsen, K. V.; Bilde, M.; Elm, J. J. Phys. Chem. A 2020, 124, 5253. doi: 10.1021/acs.jpca.0c02932 pmid: 32463668
[19]	Dohm, S.; Bursch, M.; Hansen, A.; Grimme, S. J. Chem. Theory Comput. 2020, 16, 2002. doi: 10.1021/acs.jctc.9b01266
[20]	Myllys, N.; Olenius, T.; Kurtén, T.; Vehkamäki, H.; Riipinen, I.; Elm, J. J. Phys. Chem. A 2017, 121, 4812. doi: 10.1021/acs.jpca.7b03981 pmid: 28585824
[21]	Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
[22]	Perdew, J. P.; Wang, Y. Phys. Rev. 1992, 45, 13244. doi: 10.1103/PhysRevB.45.13244
[23]	Amaro-Estrada, J. I.; Maron, L.; Ramirez-Solis, A. Phys. Chem. Chem. Phys. 2014, 16, 8455. doi: 10.1039/c3cp55339f pmid: 24668012
[24]	Castro, L.; Dommergue, A.; Renard, A.; Ferrari, C.; Ramirez-Solis, A.; Maron, L. Phys. Chem. Chem. Phys. 2011, 13, 16772. doi: 10.1039/c1cp22154j
[25]	Yoo, S.; Apra, E.; Zeng, X. C.; Xantheas, S. S. J. Phys. Chem. Lett. 2010, 1, 3122. doi: 10.1021/jz101245s
[26]	Neese, F.; Hansen, A.; Liakos, D. G. J. Chem. Phys. 2009, 131,064103.
[27]	He, Y.; Wang, Y. B. Acta Phys.-Chim. Sin. 2017, 33, 1149 (in Chinese.) doi: 10.3866/PKU.WHXB201703291
	何禹, 王一波, 物理化学学报, 2017, 33, 1149).
[28]	Najibi, A.; Goerigk, L. J. Chem. Theory Comput. 2018, 14, 5725. doi: 10.1021/acs.jctc.8b00842 pmid: 30299953
[29]	Mardirossian, N.; Pestana, L. R.; Womack, J. C.; Skylaris, C. K.; Head-Gordon, T.; Head-Gordon, M. J. Phys. Chem. Lett. 2017, 8, 35. doi: 10.1021/acs.jpclett.6b02527 pmid: 27936759
[30]	Mardirossian, N.; Gordon, M. H. J. Chem. Phys. 2016, 144,214110.
[31]	Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553. doi: 10.1080/00268977000101561
[32]	Kruse, H.; Grimme, S. J. Chem. Phys. 2012, 136,154101.
[33]	Grimme, S. Growing String Method, xTB Documentation, 2019, https://xtb-docs.readthedocs.io/en/latest/gsm.html
[34]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 16, Revision B. 01, Gaussian, Inc., Wallingford CT, 2016.
[35]	Neese, F., Software update: the ORCA program system, version 4.2 WIREs: Comput. Mol. Sci. 2018, 8,e1327.
[36]	Werner, H. J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M.; Celani, P.; Györffy, W.; Kats, D.; Korona, T.; Lindh, R.; Mitrushenkov, A.; Rauhut, G.; Shamasundar, K. R.; Adler, T. B.; Amos, R. D.; Bennie, S. J.; Bernhardsson, A.; Berning, A.; Cooper, D. L.; Deegan, M. J.O.; Dobbyn, A. J.; Eckert, F.; Goll, E.; Hampel, C.; Hesselmann, A.; Hetzer, G.; Hrenar, T.; Jansen, G.; Köppl, C.; Lee, S. J.R.; Liu, Y.; Lloyd, A. W.; Ma, Q.; Mata, R. A.; May, A. J.; McNicholas, S. J.; Meyer, W.; Miller III, T. F.; Mura, M. E.; Nicklass, A.; O’Neill, D. P.; Palmieri, P.; Peng, D.; Pflüger, K.; Pitzer, R.; Reiher, M.; Shiozaki, T.; Stoll, H.; Stone, A. J.; Tarroni, R.; Thorsteinsson, T.; Wang, M.; Welborn, M. MOLPRO, version 2018, a package of ab initio programs, http://www.molpro.net
[37]	Yang, Z. Z.; Meng, X. F.; Zhao, D. X.; Gong, L. D. Acta Chim. Sinica 2009, 67, 2074 (in Chinese.)
	杨忠志, 孟祥凤, 赵东霞, 宫利东化学学报 2009, 67, 2074).
[38]	Temelso, B.; Morrell, T. E.; Shields, R. M.; Allodi, M. A.; Wood, E. K.; Kirschner, K. N.; Castonguay, T. C.; Archer, K. A.; Shields, G. C. J. Phys. Chem. A 2012, 116, 2209. doi: 10.1021/jp2119026