Articles | Volume 24, issue 7
https://doi.org/10.5194/acp-24-4029-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-24-4029-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
04 Apr 2024
Research article |
| 04 Apr 2024
| 04 Apr 2024
Reaction of SO3 with H2SO4 and its implications for aerosol particle formation in the gas phase and at the air–water interface
Rui Wang
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Yang Cheng
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Shasha Chen
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Rongrong Li
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Yue Hu
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Xiaokai Guo
Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, PR China
Tianlei Zhang
CORRESPONDING AUTHOR
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Fengmin Song
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, PR China
Hao Li
CORRESPONDING AUTHOR
State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, PR China
Related authors
Rongrong Li, Zeyao Li, Chengyan Zhang, Rui Wang, Jihuan Yang, Heran Cui, Xuanye Li, Nini Huo, and Tianlei Zhang
EGUsphere, https://doi.org/10.5194/egusphere-2025-4960, https://doi.org/10.5194/egusphere-2025-4960, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
This study investigates the formation of hydroxymethyl hydroperoxide (HMHP) through methanesulfonic acid (MSA)-catalyzed hydrolysis of CH2OO in the gas phase and at the air-water interface. HMHP forms rapidly and stably in both environments. Further analysis shows that HMHP enhances the stability of MSA-methylamine (MA) clusters and highlights HMHP's key role in MSA-MA-HMHP nucleation, especially in urban and forested regions.
Rui Wang, Shuqin Wei, Zeyao Li, Kaiyu Xue, Rui Bai, and Tianlei Zhang
EGUsphere, https://doi.org/10.5194/egusphere-2025-4894, https://doi.org/10.5194/egusphere-2025-4894, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
This study investigates the atmospheric formation of lactic acid sulfate and its role in new particle formation, with implications for air quality and climate. The results show that lactic acid sulfate enhances particle cluster stability and promotes new particle formation, particularly in forested and agricultural regions. These findings highlight the important role of organic compounds like lactic acid sulfate in particle formation, offering insights for mitigating haze and health risks.
Rui Wang, Rongrong Li, Shasha Chen, Ruxue Mu, Changming Zhang, Xiaohui Ma, Majid Khan, and Tianlei Zhang
Atmos. Chem. Phys., 25, 5695–5709, https://doi.org/10.5194/acp-25-5695-2025, https://doi.org/10.5194/acp-25-5695-2025, 2025
Short summary
Short summary
Gaseous results indicated that SO3 hydrolysis with formic sulfuric anhydride (FSA) has a Gibbs free energy barrier as low as 1.5 kcal mol-1 and can effectively compete with other SO3 hydrolysis. Interfacial BOMD (Born–Oppenheimer molecular dynamics) simulations illustrated that FSA-mediated SO3 hydrolysis at the gas–liquid interface occurs through a stepwise mechanism and can be completed within a few picoseconds. ACDC (Atmospheric Clusters Dynamics Code) kinetic simulations indicated that FSA significantly enhances cluster formation rates in the H2SO4–NH3 system.
Hui Wang, Shuqin Wei, Jihuan Yang, Yanlong Yang, Rongrong Li, Rui Wang, Chongqin Zhu, Tianlei Zhang, and Changming Zhang
Atmos. Chem. Phys., 25, 2829–2844, https://doi.org/10.5194/acp-25-2829-2025, https://doi.org/10.5194/acp-25-2829-2025, 2025
Short summary
Short summary
In the gaseous reaction, the activation energy for the hydrolysis of HNSO2 catalyzed by MSA was only 0.8 kcal mol−1. Atmospheric Cluster Dynamic Code kinetic simulations disclosed that sulfamic acid markedly enhances the assembly of a methanesulfonic acid–methylamine-based cluster. At the air–water interface, the NH2SO3− and H3O+ ion formation mechanism and the proton exchange mechanism were observed.
Rongrong Li, Zeyao Li, Chengyan Zhang, Rui Wang, Jihuan Yang, Heran Cui, Xuanye Li, Nini Huo, and Tianlei Zhang
EGUsphere, https://doi.org/10.5194/egusphere-2025-4960, https://doi.org/10.5194/egusphere-2025-4960, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
This study investigates the formation of hydroxymethyl hydroperoxide (HMHP) through methanesulfonic acid (MSA)-catalyzed hydrolysis of CH2OO in the gas phase and at the air-water interface. HMHP forms rapidly and stably in both environments. Further analysis shows that HMHP enhances the stability of MSA-methylamine (MA) clusters and highlights HMHP's key role in MSA-MA-HMHP nucleation, especially in urban and forested regions.
Rui Wang, Shuqin Wei, Zeyao Li, Kaiyu Xue, Rui Bai, and Tianlei Zhang
EGUsphere, https://doi.org/10.5194/egusphere-2025-4894, https://doi.org/10.5194/egusphere-2025-4894, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
This study investigates the atmospheric formation of lactic acid sulfate and its role in new particle formation, with implications for air quality and climate. The results show that lactic acid sulfate enhances particle cluster stability and promotes new particle formation, particularly in forested and agricultural regions. These findings highlight the important role of organic compounds like lactic acid sulfate in particle formation, offering insights for mitigating haze and health risks.
Jialin Lu, Tianzeng Chen, Jun Liu, Huiying Xuan, Peng Zhang, Qingxin Ma, Yonghong Wang, Hao Li, Biwu Chu, and Hong He
EGUsphere, https://doi.org/10.5194/egusphere-2025-3956, https://doi.org/10.5194/egusphere-2025-3956, 2025
Short summary
Short summary
Ground-level ozone pollution in Beijing poses a serious threat to health and the environment. We ultimately discovered that insufficiently recognized processes in the atmosphere that can scavenge nitrogen dioxide are crucial. After incorporating these into the model, the prediction accuracy for Beijing ozone was dramatically improved. Our work provides more precise tools for designing cleaner air strategies in China.
Rui Wang, Rongrong Li, Shasha Chen, Ruxue Mu, Changming Zhang, Xiaohui Ma, Majid Khan, and Tianlei Zhang
Atmos. Chem. Phys., 25, 5695–5709, https://doi.org/10.5194/acp-25-5695-2025, https://doi.org/10.5194/acp-25-5695-2025, 2025
Short summary
Short summary
Gaseous results indicated that SO3 hydrolysis with formic sulfuric anhydride (FSA) has a Gibbs free energy barrier as low as 1.5 kcal mol-1 and can effectively compete with other SO3 hydrolysis. Interfacial BOMD (Born–Oppenheimer molecular dynamics) simulations illustrated that FSA-mediated SO3 hydrolysis at the gas–liquid interface occurs through a stepwise mechanism and can be completed within a few picoseconds. ACDC (Atmospheric Clusters Dynamics Code) kinetic simulations indicated that FSA significantly enhances cluster formation rates in the H2SO4–NH3 system.
Hui Wang, Shuqin Wei, Jihuan Yang, Yanlong Yang, Rongrong Li, Rui Wang, Chongqin Zhu, Tianlei Zhang, and Changming Zhang
Atmos. Chem. Phys., 25, 2829–2844, https://doi.org/10.5194/acp-25-2829-2025, https://doi.org/10.5194/acp-25-2829-2025, 2025
Short summary
Short summary
In the gaseous reaction, the activation energy for the hydrolysis of HNSO2 catalyzed by MSA was only 0.8 kcal mol−1. Atmospheric Cluster Dynamic Code kinetic simulations disclosed that sulfamic acid markedly enhances the assembly of a methanesulfonic acid–methylamine-based cluster. At the air–water interface, the NH2SO3− and H3O+ ion formation mechanism and the proton exchange mechanism were observed.
Cited articles
Abedi, M. and Farrokhpour, H.: Acidity constants of some sulfur oxoacids in aqueous solution using CCSD and MP2 methods, Dalton T., 42, 5566–5572, https://doi.org/10.1039/C3DT33056G, 2013.
Adler, T. B., Knizia, G., and Werner, H. J.: A simple and efficient CCSD(T)-F12 approximation, J. Chem. Phys., 127, 221106, https://doi.org/10.1063/1.2817618, 2007.
Akhmatskaya, E., Apps, C., Hillier, I., Masters, A., Palmer, I., Watt, N., Vincent, M., and Whitehead, J.: Hydrolysis of SO3 and ClONO2 in water clusters: A combined experimental and theoretical study, J. Am. Chem. Soc., 93, 2775–2779, 1997.
Almeida, J., Schobesberger, S., Kürten, A., Ortega, I. K., Kupiainen-Määttä, O., Praplan, A. P., Adamov, A., Amorim, A., Bianchi, F., Breitenlechner, M., David, A., Dommen, J., Donahue, N. M., Downard, A., Dunne, E., Duplissy, J., Ehrhart, S., Flagan, R. C., Franchin, A., Guida, R., Hakala, J., Hansel, A., Heinritzi, M., Henschel, H., Jokinen, T., Junninen, H., Kajos, M., Kangasluoma, J., Keskinen, H., Kupc, A., Kurtén, T., Kvashin, A. N., Laaksonen, A., Lehtipalo, K., Leiminger, M., Leppä, J., Loukonen, V., Makhmutov, V., Mathot, S., McGrath, M. J., Nieminen, T., Olenius, T., Onnela, A., Petäjä, T., Riccobono, F., Riipinen, I., Rissanen, M., Rondo, L., Ruuskanen, T., Santos, F. D., Sarnela, N., Schallhart, S., Schnitzhofer, R., Seinfeld, J. H., Simon, M., Sipilä, M., Stozhkov, Y., Stratmann, F., Tomé, A., Tröstl, J., Tsagkogeorgas, G., Vaattovaara, P., Viisanen, Y., Virtanen, A., Vrtala, A., Wagner, P. E., Weingartner, E., Wex, H., Williamson, C., Wimmer, D., Ye, P., Yli-Juuti, T., Carslaw, K. S., Kulmala, M., Curtius, J., Baltensperger, U., Worsnop, D. R., Vehkamäki, H., and Kirkby, J.: Molecular understanding of sulphuric acid–amine particle nucleation in the atmosphere, Nature, 502, 359–363, https://doi.org/10.1038/nature12663, 2013.
Anglada, J. M., Hoffman, G. J., Slipchenko, L. V., M. Costa, M., Ruiz-Lopez, M. F., and Francisco, J. S.: Atmospheric significance of water clusters and ozone–water complexes, J. Phys. Chem. A, 117, 10381–10396, 2013.
Bandyopadhyay, B., Kumar, P., and Biswas, P.: Ammonia Catalyzed Formation of Sulfuric Acid in Troposphere: The Curious Case of a Base Promoting Acid Rain, J. Phys. Chem. A, 121, 3101–3108, https://doi.org/10.1021/acs.jpca.7b01172, 2017.
Becke, A. D.: Density-functional exchange-energy approximation with correct asymptotic behavior, Phys. Rev. A, 38, 3098–3100, 1988.
Bouo, F.-X., Kouamé, J., Tchétché, Y., Kré, R., Moussé, M., Assamoi, P., Cautenet, S., and Cautenet, G.: Redistribution of free tropospheric chemical species over West Africa: Radicals (OH and HO2), peroxide (H2O2) and acids (HNO3 and H2SO4), Chemosphere, 84, 1617–1629, 2011.
Calvert, J. G., Lazrus, A., Kok, G. L., Heikes, B. G., Walega, J. G., Lind, J., and Cantrell, C. A.: Chemical mechanisms of acid generation in the troposphere, Nature, 317, 27–35, 1985.
Cao, Y., Zhou, H., Jiang, W., Chen, C. W., and Pan, W. P.: Studies of the fate of sulfur trioxide in coal-fired utility boilers based on modified selected condensation methods, Environ. Sci. Technol., 44, 3429–3434, 2010.
Chen, L. and Bhattacharya, S.: Sulfur emission from Victorian brown coal under pyrolysis, oxy-fuel combustion and gasification conditions, Environ. Sci. Technol., 47, 1729–1734, 2013.
Chen, T. and Plummer, P. L.: Ab initio MO investigation of the gas-phase reaction sulfur trioxide + water .fwdarw. sulfuric acid, J. Phys. Chem. A, 89, 3689–3693, 1985.
Chen, X., Tao, C., Zhong, L., Gao, Y., Yao, W., and Li, S.: Theoretical study on the atmospheric reaction of SO2 with the HO2 and HO2⋅H2O complex formation HSO4 and H2SO3, Chem. Phys. Lett., 608, 272–276, 2014.
Cheng, Y., Ding, C., Wang, H., Zhang, T., Wang, R., Muthiah, B., Xu, H., Zhang, Q., and Jiang, M.: Significant influence of water molecules on the SO3 + HCl reaction in the gas phase and at the air–water interface, Phys. Chem. Chem. Phys., 25, 28885–28894, https://doi.org/10.1039/D3CP03172A, 2023.
Curtius, J., Arnold, F., and Schulte, P.: Sulfuric acid measurements in the exhaust plume of a jet aircraft in flight: Implications for the sulfuric acid formation efficiency, Geophys. Res. Lett., 29, 17-11–1714, 2002.
Elm, J., Bilde, M., and Mikkelsen, K. V.: Assessment of density functional theory in predicting structures and free energies of reaction of atmospheric prenucleation clusters, J. Chem. Theory Comput., 8, 2071–2077, 2012.
Elm, J., Bilde, M., and Mikkelsen, K. V.: Influence of nucleation precursors on the reaction kinetics of methanol with the OH radical, J. Phys. Chem. A, 117, 6695–6701, 2013.
England, G. C., Zielinska, B., Loos, K., Crane, I., and Ritter, K.: Characterizing PM2. 5 emission profiles for stationary sources: comparison of traditional and dilution sampling techniques, Fuel Process. Technol., 65, 177–188, 2000.
Finlayson-Pitts, B. J. and Pitts Jr, J. N.: Atmospheric chemistry. Fundamentals and experimental techniques, John Wiley and Sons, New York, https://doi.org/10.1029/EO068i049p01643-01, 1986.
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., 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, Ö., Foresman, J. B., Ortiz, J. V., Cioslowski, J., and Fox, D. J.: Gaussian 09 Revision D.01, Gaussian Inc., Wallingford, CT, http://www.gaussian.com (last access: December 2023), 2009.
Gao, J., Wang, R., Zhang, T., Liu, F., and Wang, W.: Effect of methyl hydrogen sulfate on the formation of sulfuric acid–ammonia clusters: A theoretical study, J. Chin. Chem. Soc.-Taip., 70, 689–698, https://doi.org/10.1002/jccs.202200148, 2023.
Glowacki, D. R., Liang, C.-H., Morley, C., Pilling, M. J., and Robertson, S. H.: MESMER: an open-source master equation solver for multi-energy well reactions, J. Phys. Chem. A, 116, 9545–9560, 2012.
Goedecker, S., Teter, M., and Hutter, J.: Separable dual-space Gaussian pseudopotentials, Phys. Rev. B, 54, 1703, 1996.
Gonzalez, J., Torrent-Sucarrat, M., and Anglada, J. M.: The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4, Phys. Chem. Chem. Phys., 12, 2116–2125, 2010.
Grimme, S., Antony, J., Ehrlich, S., and Krieg, H.: A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu, J. Chem. Phys., 132, 154104, 2010.
Hartwigsen, C., Goedecker, S., and Hutter, J.: Relativistic separable dual-space Gaussian pseudopotentials from H to Rn, Phys. Rev. B, 58, 3641–3662, 1998.
Haywood, J. and Boucher, O.: Estimates of the direct and indirect radiative forcing due to tropospheric aerosols: A review, Rev. Geophys., 38, 513–543, 2000.
Hazra, M. K. and Sinha, A.: Formic acid catalyzed hydrolysis of SO3 in the gas phase: A barrierless mechanism for sulfuric acid production of potential atmospheric importance, J. Am. Chem. Soc., 133, 17444–17453, 2011.
Hofmann, M. and Schleyer, P. v. R.: Acid rain: Ab initio investigation of the H2O⋅SO3 complex and its conversion to H2SO4, J. Am. Chem. Soc., 116, 4947–4952, 1994.
Horváth, G., Horváth, I., Almousa, S. A.-D., and Telek, M.: Numerical inverse Laplace transformation using concentrated matrix exponential distributions, Perform. Evaluation, 137, 102067, https://doi.org/10.1016/j.peva.2019.102067, 2020.
Huff, A. K., Mackenzie, R. B., Smith, C. J., and Leopold, K. R.: Facile Formation of Acetic Sulfuric Anhydride: Microwave Spectrum, Internal Rotation, and Theoretical Calculations, J. Phys. Chem. A, 121, 5659–5664, https://doi.org/10.1021/acs.jpca.7b05105, 2017.
Hutter, J., Iannuzzi, M., Schiffmann, F., and VandeVondele, J.: cp2k: atomistic simulations of condensed matter systems, WIREs Comput. Mol. Sci., 4, 15–25, 2014.
Kanno, N., Tonokura, K., and Koshi, M.: Equilibrium constant of the HO2-H2O complex formation and kinetics of HO2 + HO2-H2O: Implications for tropospheric chemistry, J. Geophys. Res.-Atmos., 111, D20312, https://doi.org/10.1029/2005jd006805, 2006.
Kikuchi, R.: Environmental management of sulfur trioxide emission: impact of SO3 on human health, Environ. Manage., 27, 837–844, 2001.
Kirkby, J., Curtius, J., Almeida, J., Dunne, E., Duplissy, J., Ehrhart, S., Franchin, A., Gagné, S., Ickes, L., Kürten, A., Kupc, A., Metzger, A., Riccobono, F., Rondo, L., Schobesberger, S., Tsagkogeorgas, G., Wimmer, D., Amorim, A., Bianchi, F., Breitenlechner, M., David, A., Dommen, J., Downard, A., Ehn, M., Flagan, R. C., Haider, S., Hansel, A., Hauser, D., Jud, W., Junninen, H., Kreissl, F., Kvashin, A., Laaksonen, A., Lehtipalo, K., Lima, J., Lovejoy, E. R., Makhmutov, V., Mathot, S., Mikkilä, J., Minginette, P., Mogo, S., Nieminen, T., Onnela, A., Pereira, P., Petäjä, T., Schnitzhofer, R., Seinfeld, J. H., Sipilä, M., Stozhkov, Y., Stratmann, F., Tomé, A., Vanhanen, J., Viisanen, Y., Vrtala, A., Wagner, P. E., Walther, H., Weingartner, E., Wex, H., Winkler, P. M., Carslaw, K. S., Worsnop, D. R., Baltensperger, U., and Kulmala, M.: Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation, Nature, 476, 429–433, https://doi.org/10.1038/nature10343, 2011.
Knizia, G., Adler, T. B., and Werner, H.-J.: Simplified CCSD(T)-F12 methods: Theory and benchmarks, J. Chem. Phys., 130, 054104, https://doi.org/10.1063/1.3054300, 2009.
Kuang, C., McMurry, P. H., McCormick, A. V., and Eisele, F.: Dependence of nucleation rates on sulfuric acid vapor concentration in diverse atmospheric locations, J. Geophys. Res.-Atmos., 113, D10209, https://doi.org/10.1029/2007JD009253, 2008.
Kuczkowski, R. L., Suenram, R. D., and Lovas, F. J.: Microwave spectrum, structure, and dipole moment of sulfuric acid, J. Am. Chem. Soc., 103, 2561–2566, 1981.
Kulmala, M., Vehkamäki, H., Petäjä, T., Dal Maso, M., Lauri, A., Kerminen, V. M., Birmili, W., and McMurry, P. H.: Formation and growth rates of ultrafine atmospheric particles: a review of observations, J. Aerosol Sci., 35, 143–176, https://doi.org/10.1016/j.jaerosci.2003.10.003, 2004.
Kumar, M., Zhong, J., Francisco, J. S., and Zeng, X. C.: Criegee intermediate-hydrogen sulfide chemistry at the air/water interface, Chem. Sci., 8, 5385–5391, 2017.
Kumar, M., Zhong, J., Zeng, X. C., and Francisco, J. S.: Reaction of Criegee Intermediate with Nitric Acid at the Air–Water Interface, J. Am. Chem. Soc., 140, 4913–4921, https://doi.org/10.1021/jacs.8b01191, 2018.
Larson, L. J., Kuno, M., and Tao, F.-M.: Hydrolysis of sulfur trioxide to form sulfuric acid in small water clusters, J. Chem. Phys., 112, 8830–8838, 2000.
Lee, C., Yang, W., and Parr, R. G.: Development of the Colle–Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B, 37, 785–789, 1988.
Li, H., Zhong, J., Vehkamäki, H., Kurtén, T., Wang, W., Ge, M., Zhang, S., Li, Z., Zhang, X., Francisco, J. S., and Zeng, X. C.: Self-Catalytic Reaction of SO3 and NH3 To Produce Sulfamic Acid and Its Implication to Atmospheric Particle Formation, J. Am. Chem. Soc., 140, 11020–11028, https://doi.org/10.1021/jacs.8b04928, 2018.
Li, K., Song, X., Zhu, T., Wang, C., Sun, X., Ning, P., and Tang, L.: Mechanistic and kinetic study on the catalytic hydrolysis of COS in small clusters of sulfuric acid, Environ. Pollut., 232, 615–623, https://doi.org/10.1016/j.envpol.2017.10.004, 2018.
Li, L., Kumar, M., Zhu, C., Zhong, J., Francisco, J. S., and Zeng, X. C.: Near-barrierless ammonium bisulfate formation via a loop-structure promoted proton-transfer mechanism on the surface of water, J. Am. Chem. Soc., 138, 1816–1819, 2016.
Liu, J., Fang, S., Wang, Z., Yi, W., Tao, F. M., and Liu, J. Y.: Hydrolysis of sulfur dioxide in small clusters of sulfuric acid: Mechanistic and kinetic study, Environ. Sci. Technol., 49, 13112–13120, 2015.
Liu, J., Liu, L., Rong, H., and Zhang, X.: The potential mechanism of atmospheric new particle formation involving amino acids with multiple functional groups, Phys. Chem. Chem. Phys., 23, 10184–10195, https://doi.org/10.1039/D0CP06472F, 2021.
Liu, L., Zhong, J., Vehkamäki, H., Kurtén, T., Du, L., Zhang, X., Francisco, J. S., and Zeng, X. C.: Unexpected quenching effect on new particle formation from the atmospheric reaction of methanol with SO3, P. Natl. Acad. Sci. USA, 116, 24966–24971, 2019.
Liu, L., Yu, F., Tu, K., Yang, Z., and Zhang, X.: Influence of atmospheric conditions on the role of trifluoroacetic acid in atmospheric sulfuric acid–dimethylamine nucleation, Atmos. Chem. Phys., 21, 6221–6230, https://doi.org/10.5194/acp-21-6221-2021, 2021.
Loerting, T. and Liedl, K. R.: Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO3 to H2SO4, P. Natl. Acad. Sci. USA, 97, 8874–8878, 2000.
Lohmann, U. and Feichter, J.: Global indirect aerosol effects: a review, J. Atmos. Chem. Phys., 5, 715–737, 2005.
Long, B., Long, Z. W., Wang, Y.-b., Tan, X. F., Han, Y. H., Long, C. Y., Qin, S. J., and Zhang, W. J.: Formic Acid Catalyzed Gas-Phase Reaction of H2O with SO3 and the Reverse Reaction: A Theoretical Study, ChemPhysChem, 13, 323–329, https://doi.org/10.1002/cphc.201100558, 2012.
Long, B., Chang, C. R., Long, Z. W., Wang, Y. B., Tan, X. F., and Zhang, W. J.: Nitric acid catalyzed hydrolysis of SO3 in the formation of sulfuric acid: A theoretical study, Chem. Phys. Lett., 581, 26–29, 2013a.
Long, B., Tan, X. F., Chang, C. R., Zhao, W. X., Long, Z. W., Ren, D. S., and Zhang, W. J.: Theoretical studies on gas-phase reactions of sulfuric acid catalyzed hydrolysis of formaldehyde and formaldehyde with sulfuric acid and H2SO4⋯H2O complex, J. Phys. Chem. A, 117, 5106–5116, 2013b.
Lv, G. and Sun, X. M.: The role of air–water interface in the SO3 hydration reaction, Atmos. Environ., 230, 117514, https://doi.org/10.1016/j.atmosenv.2020.117514, 2020.
Lv, G., Sun, X., Zhang, C., and Li, M.: Understanding the catalytic role of oxalic acid in SO3 hydration to form H2SO4 in the atmosphere, Atmos. Chem. Phys., 19, 2833–2844, https://doi.org/10.5194/acp-19-2833-2019, 2019.
Ma, X., Zhao, X., Ding, Z., Wang, W., Wei, Y., Xu, F., Zhang, Q., and Wang, W.: Determination of the amine-catalyzed SO3 hydrolysis mechanism in the gas phase and at the air–water interface, Chemosphere, 252, 126292, https://doi.org/10.1016/j.chemosphere.2020.126292, 2020.
Mackenzie, R. B., Dewberry, C. T., and Leopold, K. R.: Gas phase observation and microwave spectroscopic characterization of formic sulfuric anhydride, Science, 349, 58–61, 2015.
Mardirossian, N. and Head-Gordon, M.: How accurate are the Minnesota density functionals for noncovalent interactions, isomerization energies, thermochemistry, and barrier heights involving molecules composed of main-group elements?, J. Chem. Theory Comput., 12, 4303–4325, 2016.
McGrath, M. J., Olenius, T., Ortega, I. K., Loukonen, V., Paasonen, P., Kurtén, T., Kulmala, M., and Vehkamäki, H.: Atmospheric Cluster Dynamics Code: a flexible method for solution of the birth-death equations, Atmos. Chem. Phys., 12, 2345–2355, https://doi.org/10.5194/acp-12-2345-2012, 2012.
Miller, J. A. and Klippenstein, S. J.: Master equation methods in gas phase chemical kinetics, J. Phys. Chem. A, 110, 10528–10544, 2006.
Mitsui, Y., Imada, N., Kikkawa, H., and Katagawa, A.: Study of Hg and SO3 behavior in flue gas of oxy-fuel combustion system, Int. J. Greenh. Gas Con., 5, S143–S150, 2011.
Morokuma, K. and Muguruma, C.: Ab initio molecular orbital study of the mechanism of the gas phase reaction SO3 + H2O: Importance of the second water molecule, J. Am. Chem. Soc., 116, 10316–10317, 1994.
Neese, F.: The ORCA program system, WIREs Comput. Mol. Sci., 2, 73–78, https://doi.org/10.1002/wcms.81, 2012.
Otto, A. H. and Steudel, R.: Gas-Phase Structures and Acidities of the Sulfur Oxoacids H2SnO6 (n = 2–4) and H2S2O7, Eur. J. Inorg. Chem., 2001, 3047–3054, 2001.
Pérez-Ríos, J., Ragole, S., Wang, J., and Greene, C. H.: Comparison of classical and quantal calculations of helium three-body recombination, J. Chem. Phys., 140, 044307, https://doi.org/10.1063/1.4861851, 2014.
Pöschl, U.: Atmospheric aerosols: composition, transformation, climate and health effects, Angew. Chem. Int. Edit., 44, 7520–7540, 2005.
Pöschl, U. and Shiraiwa, M.: Multiphase chemistry at the atmosphere-biosphere interface influencing climate and public health in the anthropocene, Chem. Rev., 115, 4440–4475, 2015.
Renard, J. J., Calidonna, S. E., and Henley, M. V.: Fate of ammonia in the atmosphere—a review for applicability to hazardous releases, J. Hazard. Mater., 108, 29–60, 2004.
Riipinen, I., Sihto, S.-L., Kulmala, M., Arnold, F., Dal Maso, M., Birmili, W., Saarnio, K., Teinilä, K., Kerminen, V.-M., Laaksonen, A., and Lehtinen, K. E. J.: Connections between atmospheric sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä, Atmos. Chem. Phys., 7, 1899–1914, https://doi.org/10.5194/acp-7-1899-2007, 2007.
Rong, H., Liu, L., Liu, J., and Zhang, X.: Glyoxylic sulfuric anhydride from the gas-phase reaction between glyoxylic acid and SO3: a potential nucleation precursor, J. Phys. Chem. A, 124, 3261–3268, 2020.
Shampine, L. F. and Reichelt, M. W.: The MATLAB ODE Suite, J. Sci. Comput., 18, 1–22, https://doi.org/10.1137/s1064827594276424, 1997.
Sihto, S.-L., Kulmala, M., Kerminen, V.-M., Dal Maso, M., Petäjä, T., Riipinen, I., Korhonen, H., Arnold, F., Janson, R., Boy, M., Laaksonen, A., and Lehtinen, K. E. J.: Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms, Atmos. Chem. Phys., 6, 4079–4091, https://doi.org/10.5194/acp-6-4079-2006, 2006.
Sipilä, M., Berndt, T., Petäjä, T., Brus, D., Vanhanen, J., Stratmann, F., Patokoski, J., Mauldin III, R. L., Hyvärinen, A.-P., and Lihavainen, H.: The role of sulfuric acid in atmospheric nucleation, Science, 327, 1243–1246, 2010.
Smith, C. J., Huff, A. K., Mackenzie, R. B., and Leopold, K. R.: Observation of Two Conformers of Acrylic Sulfuric Anhydride by Microwave Spectroscopy, J. Phys. Chem. A, 121, 9074–9080, https://doi.org/10.1021/acs.jpca.7b09833, 2017.
Starik, A., Savel'Ev, A., Titova, N., Loukhovitskaya, E., and Schumann, U.: Effect of aerosol precursors from gas turbine engines on the volatile sulfate aerosols and ion clusters formation in aircraft plumes, Phys. Chem. Chem. Phys., 6, 3426–3436, 2004.
Steudel, R.: Sulfuric acid from sulfur trioxide and water—a surprisingly complex reaction, Angew. Chem. Int. Edit., 34, 1313–1315, 1995.
Stewart, J.: MOPAC2016, Stewart computational chemistry, Colorado Springs, CO, OpenMOPAC, 2016.
Stewart, J. J.: Optimization of parameters for semiempirical methods VI: more modifications to the NDDO approximations and re-optimization of parameters, J. Mol. Model., 19, 1–32, https://doi.org/10.1007/s00894-012-1667-x, 2013.
Stewart, J. J. P.: Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements, J. Mol. Model., 13, 1173–1213, https://doi.org/10.1007/s00894-007-0233-4, 2007.
Stone, D. and Rowley, D. M.: Kinetics of the gas phase HO2 self-reaction: Effects of temperature, pressure, water and methanol vapours, Phys. Chem. Chem. Phys., 7, 2156–2163, https://doi.org/10.1039/B502673C, 2005.
Tan, X. F., Long, B., Ren, D. S., Zhang, W. J., Long, Z. W., and Mitchell, E.: Atmospheric chemistry of CH3CHO: the hydrolysis of CH3CHO catalyzed by H2SO4, Phys. Chem. Chem. Phys., 20, 7701–7709, 2018.
Tilgner, A., Schaefer, T., Alexander, B., Barth, M., Collett Jr., J. L., Fahey, K. M., Nenes, A., Pye, H. O. T., Herrmann, H., and McNeill, V. F.: Acidity and the multiphase chemistry of atmospheric aqueous particles and clouds, Atmos. Chem. Phys., 21, 13483–13536, https://doi.org/10.5194/acp-21-13483-2021, 2021.
Torrent-Sucarrat, M., Francisco, J. S., and Anglada, J. M.: Sulfuric acid as autocatalyst in the formation of sulfuric acid, J. Am. Chem. Soc., 134, 20632–20644, 2012.
VandeVondele, J. and Hutter, J.: Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases, J. Chem. Phys., 127, 114105, https://doi.org/10.1063/1.2770708, 2007.
Viegas, L. P. and Varandas, A. J.: Can water be a catalyst on the HO2 + H2O + O3 reactive cluster?, Chem. Phys., 399, 17–22, 2012.
Viegas, L. P. and Varandas, A. J.: The HO2 + (H2O)n + O3 reaction: an overview and recent developments, Eur. Phys. J. D, 70, 1–9, 2016.
Wayne, R. P.: Chemistry of Atmospheres. An Introduction to the Chemistry of the Atmospheres of Earth, the Planets, and Their Satellites, 3rd edn., Oxford University Press, https://doi.org/10.1021/ja004780n, 2000.
Weber, R., McMurry, P., Eisele, F., and Tanner, D.: Measurement of expected nucleation precursor species and 3–500-nm diameter particles at Mauna Loa observatory, Hawaii, J. Atmos. Sci., 52, 2242–2257, 1995.
Weber, R., Marti, J., McMurry, P., Eisele, F., Tanner, D., and Jefferson, A.: Measured atmospheric new particle formation rates: Implications for nucleation mechanisms, Chem. Eng. Commun., 151, 53–64, 1996.
Weber, R., Chen, G., Davis, D., Mauldin III, R., Tanner, D., Eisele, F., Clarke, A., Thornton, D., and Bandy, A.: Measurements of enhanced H2SO4 and 3–4 nm particles near a frontal cloud during the First Aerosol Characterization Experiment (ACE 1), J. Geophys. Res.-Atmos., 106, 24107–24117, 2001.
Yang, Y., Liu, L., Wang, H., and Zhang, X.: Molecular-Scale Mechanism of Sequential Reaction of Oxalic Acid with SO3: Potential Participator in Atmospheric Aerosol Nucleation, J. Phys. Chem. A, 125, 4200–4208, 2021.
Yao, L., Garmash, O., Bianchi, F., Zheng, J., Yan, C., Kontkanen, J., Junninen, H., Mazon, S. B., Ehn, M., Paasonen, P., Sipilä, M., Wang, M., Wang, X., Xiao, S., Chen, H., Lu, Y., Zhang, B., Wang, D., Fu, Q., Geng, F., Li, L., Wang, H., Qiao, L., Yang, X., Chen, J., Kerminen, V.-M., Petäjä, T., Worsnop, D. R., Kulmala, M., and Wang, L.: Atmospheric new particle formation from sulfuric acid and amines in a Chinese megacity, Science, 361, 278–281, https://doi.org/10.1126/science.aao4839, 2018.
Yao, L., Fan, X., Yan, C., Kurtén, T., Daellenbach, K. R., Li, C., Wang, Y., Guo, Y., Dada, L., Rissanen, M. P., Cai, J., Tham, Y. J., Zha, Q., Zhang, S., Du, W., Yu, M., Zheng, F., Zhou, Y., Kontkanen, J., Chan, T., Shen, J., Kujansuu, J. T., Kangasluoma, J., Jiang, J., Wang, L., Worsnop, D. R., Petäjä, T., Kerminen, V. M., Liu, Y., Chu, B., He, H., Kulmala, M., and Bianchi, F.: Unprecedented Ambient Sulfur Trioxide (SO3) Detection: Possible Formation Mechanism and Atmospheric Implications, Environ. Sci. Technol. Lett., 7, 809–818, https://doi.org/10.1021/acs.estlett.0c00615, 2020.
Zhao, Y. and Truhlar, D. G.: The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals, Theor. Chem. Acc., 120, 215–241, 2008.
Zhang, H., Kupiainen-Määttä, O., Zhang, X., Molinero, V., Zhang, Y., and Li, Z.: The enhancement mechanism of glycolic acid on the formation of atmospheric sulfuric acid–ammonia molecular clusters, J. Chem. Phys., 146, 184308, https://doi.org/10.1063/1.4982929, 2017.
Zhang, H., Li, H., Liu, L., Zhang, Y., Zhang, X., and Li, Z.: The potential role of malonic acid in the atmospheric sulfuric acid–ammonia clusters formation, Chemosphere, 203, 26–33, 2018.
Zhang, J. and Dolg, M.: ABCluster: the artificial bee colony algorithm for cluster global optimization, Phys. Chem. Chem. Phys., 17, 24173–24181, https://doi.org/10.1039/C5CP04060D, 2015.
Zhang, J. and Dolg, M.: Global optimization of clusters of rigid molecules using the artificial bee colony algorithm, Phys. Chem. Chem. Phys., 18, 3003–3010, https://doi.org/10.1039/C5CP06313B, 2016.
Zhang, R., Khalizov, A., Wang, L., Hu, M., and Xu, W.: Nucleation and growth of nanoparticles in the atmosphere, Chem. Rev., 112, 1957–2011, 2012.
Zhang, R., Wang, G., Guo, S., Zamora, M. L., Ying, Q., Lin, Y., Wang, W., Hu, M., and Wang, Y.: Formation of urban fine particulate matter, Chem. Rev., 115, 3803–3855, 2015.
Zhang, R., Shen, J., Xie, H.-B., Chen, J., and Elm, J.: The role of organic acids in new particle formation from methanesulfonic acid and methylamine, Atmos. Chem. Phys., 22, 2639–2650, https://doi.org/10.5194/acp-22-2639-2022, 2022.
Zhong, J., Zhao, Y., Li, L., Li, H., Francisco, J. S., and Zeng, X. C.: Interaction of the NH2 Radical with the Surface of a Water Droplet, J. Am. Chem. Soc., 137, 12070–12078, https://doi.org/10.1021/jacs.5b07354, 2015.
Zhong, J., Kumar, M., Zhu, C. Q., Francisco, J. S., and Zeng, X. C.: Frontispiece: Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces, Angew. Chem. Int. Edit., 56, 7740–7744, https://doi.org/10.1002/anie.201782761, 2017a.
Zhong, J., Zhu, C., Li, L., Richmond, G. L., Francisco, J. S., and Zeng, X. C.: Interaction of SO2 with the Surface of a Water Nanodroplet, J. Am. Chem. Soc., 139, 17168–17174, 2017b.
Zhong, J., Kumar, M., Francisco, J. S., and Zeng, X. C.: Insight into chemistry on cloud/aerosol water surfaces, Accounts Chem. Res., 51, 1229–1237, 2018.
Zhong, J., Li, H., Kumar, M., Liu, J., Liu, L., Zhang, X., Zeng, X. C., and Francisco, J. S.: Mechanistic Insight into the Reaction of Organic Acids with SO3 at the Air–Water Interface, Angew. Chem. Int. Edit., 131, 8439-8443, 2019.
Zhu, C., Kumar, M., Zhong, J., Li, L., Francisco, J. S., and Zeng, X. C.: New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface, J. Am. Chem. Soc., 138, 11164–11169, https://doi.org/10.1021/jacs.6b04338, 2016.
Zhu, C., Kais, S., Zeng, X. C., Francisco, J. S., and Gladich, I.: Interfaces select specific stereochemical conformations: the isomerization of glyoxal at the liquid water interface, J. Am. Chem. Soc., 139, 27–30, 2017.
Zhuang, Y. and Pavlish, J. H.: Fate of hazardous air pollutants in oxygen-fired coal combustion with different flue gas recycling, Environ. Sci. Technol., 46, 4657–4665, 2012.
Short summary
We used quantum chemical calculations, Born–Oppenheimer molecular dynamics simulations, and the ACDC kinetic model to characterize SO3–H2SO4 interaction in the gas phase and at the air–water interface and to study the effect of H2S2O7 on H2SO4–NH3-based clusters. The work expands our understanding of new pathways for the loss of SO3 in acidic polluted areas and helps reveal some missing sources of NPF in metropolitan industrial regions and understand the atmospheric organic–sulfur cycle better.
We used quantum chemical calculations, Born–Oppenheimer molecular dynamics simulations, and the...
Altmetrics
Final-revised paper
Preprint