Articles | Volume 26, issue 10
https://doi.org/10.5194/acp-26-6973-2026
© Author(s) 2026. 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-26-6973-2026
© Author(s) 2026. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
22 May 2026
Research article |
| 22 May 2026
| 22 May 2026
Reactions of carbonyl oxide with aldehydes: accurate electronic structure methods, kinetic insights, and atmospheric implications
Chaolu Xie
College of Physics and Mechatronic Engineering, Guizhou Minzu University, Guiyang 550025, China
College of Physics and Mechatronic Engineering, Guizhou Minzu University, Guiyang 550025, China
College of Materials Science and Engineering, Guizhou Minzu University, Guiyang 550025, China
Related authors
Chaolu Xie, Shunyu Li, and Bo Long
Atmos. Chem. Phys., 25, 17399–17412, https://doi.org/10.5194/acp-25-17399-2025, https://doi.org/10.5194/acp-25-17399-2025, 2025
Short summary
Short summary
Hydroxyacetonitrile is very important in the atmosphere, However, its chemical transformations are unclear. We develop theoretical methods and strategies to find a new reaction route for the sink of hydroxyacetonitrile by the reaction with Criegee intermediate. Moreover, in this study, the quantitative kinetics are also obtained, which improve the accuracy of atmospheric models. The reactions also provide further insights into the oxidation capacity of Criegee intermediates.
Zegang Dong, Chaolu Xie, and Bo Long
Atmos. Chem. Phys., 25, 14315–14331, https://doi.org/10.5194/acp-25-14315-2025, https://doi.org/10.5194/acp-25-14315-2025, 2025
Short summary
Short summary
Perfluoroaldehydes are important products formed in the atmospheric oxidation of fluorinated compounds. However, their degradation routes are not clear. Here, we find a rapid route for the degradation of linear perfluoroaldehydes by hydroperoxy radical. The chemical processes are dominant over the corresponding oxidation processes by hydroxyl radical. The present findings are of great importance for elucidating the chemical transformation of linear perfluoroaldehydes in the atmosphere.
Chaolu Xie, Shunyu Li, and Bo Long
Atmos. Chem. Phys., 25, 17399–17412, https://doi.org/10.5194/acp-25-17399-2025, https://doi.org/10.5194/acp-25-17399-2025, 2025
Short summary
Short summary
Hydroxyacetonitrile is very important in the atmosphere, However, its chemical transformations are unclear. We develop theoretical methods and strategies to find a new reaction route for the sink of hydroxyacetonitrile by the reaction with Criegee intermediate. Moreover, in this study, the quantitative kinetics are also obtained, which improve the accuracy of atmospheric models. The reactions also provide further insights into the oxidation capacity of Criegee intermediates.
Zegang Dong, Chaolu Xie, and Bo Long
Atmos. Chem. Phys., 25, 14315–14331, https://doi.org/10.5194/acp-25-14315-2025, https://doi.org/10.5194/acp-25-14315-2025, 2025
Short summary
Short summary
Perfluoroaldehydes are important products formed in the atmospheric oxidation of fluorinated compounds. However, their degradation routes are not clear. Here, we find a rapid route for the degradation of linear perfluoroaldehydes by hydroperoxy radical. The chemical processes are dominant over the corresponding oxidation processes by hydroxyl radical. The present findings are of great importance for elucidating the chemical transformation of linear perfluoroaldehydes in the atmosphere.
Qinghao Guo, Haofei Zhang, Bo Long, Lehui Cui, Yiyang Sun, Hao Liu, Yaxin Liu, Yunting Xiao, Pingqing Fu, and Jialei Zhu
Atmos. Chem. Phys., 25, 9249–9262, https://doi.org/10.5194/acp-25-9249-2025, https://doi.org/10.5194/acp-25-9249-2025, 2025
Short summary
Short summary
Limonene, a natural compound from plants, reacts with pollutants to form airborne particles that influence air quality and climate. Using advanced models with explicit chemical mechanisms, we show how different reaction pathways shape organonitrate formation, with some increasing and others decreasing particle levels. This approach enhances predictions of pollution and climate impacts while deepening our understanding of how natural and human-made emissions interact in the atmosphere.
Cited articles
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.
Atkinson, R. and Pitts Jr., J. N.: Kinetics of the reactions of the OH radical with HCHO and CH3CHO over the temperature range 299–426 K, J. Chem. Phys., 68, 3581–3584, https://doi.org/10.1063/1.436215, 1978.
Bao, J., Zhang, X., Wu, Z., Zhou, L., Qian, J., Tan, Q., Yang, F., Chen, J., Li, Y., Liu, H., Deng, L., and Li, H.: Atmospheric carbonyl compounds are crucial in regional ozone heavy pollution: insights from the Chengdu Plain Urban Agglomeration, China, Atmos. Chem. Phys., 25, 1899–1916, https://doi.org/10.5194/acp-25-1899-2025, 2025.
Bao, J. L., Zhang, X., and Truhlar, D. G.: Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation, Phys. Chem. Chem. Phys., 18, 16659–16670, https://doi.org/10.1039/C6CP02765B, 2016a.
Bao, J. L., Zhang, X., and Truhlar, D. G.: Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory, Proc. Natl. Acad. Sci., 113, 13606–13611, https://doi.org/10.1073/pnas.1616208113, 2016b.
Bari, M. A. and Kindzierski, W. B.: Ambient volatile organic compounds (VOCs) in Calgary, Alberta: Sources and screening health risk assessment, Sci. Total Environ., 627–640, https://doi.org/10.1016/j.scitotenv.2018.03.023, 2018.
Berndt, T., Jokinen, T., Sipilä, M., Mauldin, R. L., Herrmann, H., Stratmann, F., Junninen, H., and Kulmala, M.: H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature, Atmos. Environ., 89, 603–612, https://doi.org/10.1016/j.atmosenv.2014.02.062, 2014.
Berndt, T., Kaethner, R., Voigtländer, J., Stratmann, F., Pfeifle, M., Reichle, P., Sipilä, M., Kulmala, M., and Olzmann, M.: Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditions, Phys. Chem. Chem. Phys., 17, 19862–19873, https://doi.org/10.1039/C5CP02224J, 2015.
Bey, I., Jacob, D. J., Yantosca, R. M., Logan, J. A., Field, B. D., Fiore, A. M., Li, Q., Liu, H. Y., Mickley, L. J., and Schultz, M. G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res.-Atmos., 106, 23073–23095, https://doi.org/10.1029/2001JD000807, 2001.
Bischoff, F. A., Wolfsegger, S., Tew, D. P., and Klopper, W.: Assessment of basis sets for F12 explicitly-correlated molecular electronic-structure methods, Mol. Phys., 107, 963–975, https://doi.org/10.1080/00268970802708942, 2009.
Bossmeyer, J., Brauers, T., Richter, C., Rohrer, F., Wegener, R., and Wahner, A.: Simulation chamber studies on the NO3 chemistry of atmospheric aldehydes, Geophys. Res. Lett., 33, https://doi.org/10.1029/2006GL026778, 2006.
Boy, M., Mogensen, D., Smolander, S., Zhou, L., Nieminen, T., Paasonen, P., Plass-Dülmer, C., Sipilä, M., Petäjä, T., Mauldin, L., Berresheim, H., and Kulmala, M.: Oxidation of SO2 by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations, Atmos. Chem. Phys., 13, 3865–3879, https://doi.org/10.5194/acp-13-3865-2013, 2013.
Cabañas, B., Martín, P., Salgado, S., Ballesteros, B., and Martínez, E.: An experimental study on the temperature dependence for the gas-phase reactions of NO3 radical with a series of aliphatic aldehydes, J. Atmos. Chem., 40, 23–39, https://doi.org/10.1023/A:1010797424283, 2001.
Cabezas, C. and Endo, Y.: The Criegee intermediate-formic acid reaction explored by rotational spectroscopy, Phys. Chem. Chem. Phys., 21, 18059–18064, https://doi.org/10.1039/C9CP03001H, 2019.
Canneaux, S., Bohr, F., and Henon, E.: KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results, J. Comput. Chem., 35, 82–93, https://doi.org/10.1002/jcc.23470, 2014.
Chan, B. and Radom, L.: W2X and W3X-L: cost-effective approximations to W2 and W4 with kJ mol−1 accuracy, J. Chem. Theory Comput., 11, 2109–2119, https://doi.org/10.1021/acs.jctc.5b00135, 2015.
Chandra, A. K., Uchimaru, T., and Sugie, M.: Kinetics of hydrogen abstraction reactions of CF3CHO, CF2ClCHO, CFCl2CHO and CCl3CHO with OH Radicals: An ab initio study, Phys. Chem. Chem. Phys., 3, 3961–3966, https://doi.org/10.1039/B104904F, 2001.
Chen, W. T., Shao, M., Lu, S. H., Wang, M., Zeng, L. M., Yuan, B., and Liu, Y.: Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model, Atmos. Chem. Phys., 14, 3047–3062, https://doi.org/10.5194/acp-14-3047-2014, 2014.
Chhantyal-Pun, R., Khan, M. A. H., Zachhuber, N., Percival, C. J., Shallcross, D. E., and Orr-Ewing, A. J.: Impact of Criegee intermediate reactions with peroxy radicals on tropospheric organic aerosol, ACS Earth Space Chem., 4, 1743–1755, https://doi.org/10.1021/acsearthspacechem.0c00147, 2020.
Chung, C.-A., Su, J. W., and Lee, Y.-P.: Detailed mechanism and kinetics of the reaction of Criegee intermediate CH2OO with HCOOH investigated via infrared identification of conformers of hydroperoxymethyl formate and formic acid anhydride, Phys. Chem. Chem. Phys., 21, 21445–21455, https://doi.org/10.1039/C9CP04168K, 2019.
Cornwell, Z. A., Enders, J. J., Harrison, A. W., and Murray, C.: Temperature-dependent kinetics of the reactions of CH2OO with acetone, biacetyl, and acetylacetone, Int. J. Chem. Kinet., 55, 154–166, https://doi.org/10.1002/kin.21625, 2023.
Criegee, R.: Mechanism of Ozonolysis, Angew. Chem. Int. Ed., 14, 745–752, https://doi.org/10.1002/anie.197507451, 1975.
Criegee, R. and Wenner, G.: Die Ozonisierung des 9,10-Oktalins, Justus Liebigs Ann. Chem., 564, 9–15, https://doi.org/10.1002/jlac.19495640103, 1949.
D'Anna, B., Andresen, Ø., Gefen, Z., and Nielsen, C. J.: Kinetic study of OH and NO3 radical reactions with 14 aliphatic aldehydes, Phys. Chem. Chem. Phys., 3, 3057–3063, https://doi.org/10.1039/B103623H, 2001.
Debnath, A. and Rajakumar, B.: Experimental and theoretical study of Criegee intermediate (CH2OO) reactions with n-butyraldehyde and isobutyraldehyde: kinetics, implications and atmospheric fate, Phys. Chem. Chem. Phys., 26, 6872–6884, https://doi.org/10.1039/D3CP05482A, 2024.
Ding, D.-P. and Long, B.: Reaction between propionaldehyde and hydroxyperoxy radical in the atmosphere: A reaction route for the sink of propionaldehyde and the formation of formic acid, Atmos. Environ., 284, 119202, https://doi.org/10.1016/j.atmosenv.2022.119202, 2022.
Edwards, P. M., Brown, S. S., Roberts, J. M., Ahmadov, R., Banta, R. M., deGouw, J. A., Dubé, W. P., Field, R. A., Flynn, J. H., Gilman, J. B., Graus, M., Helmig, D., Koss, A., Langford, A. O., Lefer, B. L., Lerner, B. M., Li, R., Li, S.-M., McKeen, S. A., Murphy, S. M., Parrish, D. D., Senff, C. J., Soltis, J., Stutz, J., Sweeney, C., Thompson, C. R., Trainer, M. K., Tsai, C., Veres, P. R., Washenfelder, R. A., Warneke, C., Wild, R. J., Young, C. J., Yuan, B., and Zamora, R.: High winter ozone pollution from carbonyl photolysis in an oil and gas basin, Nature, 514, 351–354, https://doi.org/10.1038/nature13767, 2014.
Elsamra, R. M. I., Jalan, A., Buras, Z. J., Middaugh, J. E., and Green, W. H.: Temperature- and Pressure-Dependent Kinetics of CH2OO + CH3COCH3 and CH2OO + CH3CHO: Direct Measurements and Theoretical Analysis, Int. J. Chem. Kinet., 48, 474–488, https://doi.org/10.1002/kin.21007, 2016.
Enders, J. J., Cornwell, Z. A., Harrison, A. W., and Murray, C.: Temperature-Dependent Kinetics of the Reactions of the Criegee Intermediate CH2OO with Aliphatic Aldehydes, J. Phys. Chem. A, 128, 7879–7888, https://doi.org/10.1021/acs.jpca.4c04990, 2024.
Fernández-Ramos, A., Miller, J. A., Klippenstein, S. J., and Truhlar, D. G.: Modeling the Kinetics of Bimolecular Reactions, Chem. Rev., 106, 4518–4584, https://doi.org/10.1021/cr050205w, 2006.
Foreman, E. S., Kapnas, K. M., and Murray, C.: Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3: Kinetics and Atmospheric Implications, Angew. Chem. Int. Ed., 55, 10419–10422, https://doi.org/10.1002/anie.201604662, 2016.
Gao, Q., Shen, C., Zhang, H., Long, B., and Truhlar, D. G.: Quantitative kinetics reveal that reactions of HO2 are a significant sink for aldehydes in the atmosphere and may initiate the formation of highly oxygenated molecules via autoxidation, Phys. Chem. Chem. Phys., 26, 16160–16174, https://doi.org/10.1039/D4CP00693C, 2024.
Garrett, B. C. and Truhlar, D. G.: Canonical unified statistical model. Classical mechanical theory and applications to collinear reactions, J. Chem. Phys., 76, 1853–1858, https://doi.org/10.1063/1.443157, 1982.
Gelaro, R., McCarty, W., Suárez, M. J., Todling, R., Molod, A., Takacs, L., Randles, C. A., Darmenov, A., Bosilovich, M. G., Reichle, R., Wargan, K., Coy, L., Cullather, R., Draper, C., Akella, S., Buchard, V., Conaty, A., da Silva, A. M., Gu, W., Kim, G.-K., Koster, R., Lucchesi, R., Merkova, D., Nielsen, J. E., Partyka, G., Pawson, S., Putman, W., Rienecker, M., Schubert, S. D., Sienkiewicz, M., and Zhao, B.: The Modern-Era Retrospective Analysis for Research and Applications, Version 2 (MERRA-2), J. Clim., 30, 5419–5454, https://doi.org/10.1175/JCLI-D-16-0758.1, 2017.
Georgievskii, Y. and Klippenstein, S. J.: Variable reaction coordinate transition state theory: Analytic results and application to the C2H3+H→C2H4 reaction, J. Chem. Phys., 118, 5442–5455, https://doi.org/10.1063/1.1539035, 2003.
Georgievskii, Y., Miller, J. A., Burke, M. P., and Klippenstein, S. J.: Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions, J. Phys. Chem. A, 117, 12146–12154, https://doi.org/10.1021/jp4060704, 2013.
Grosjean, D., Swanson, R. D., and Ellis, C.: Carbonyls in Los Angeles air: Contribution of direct emissions and photochemistry, Sci. Total Environ., 29, 65–85, https://doi.org/10.1016/0048-9697(83)90034-7, 1983.
Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions, Geosci. Model Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Győrffy, W. and Werner, H.-J.: Analytical energy gradients for explicitly correlated wave functions. II. Explicitly correlated coupled cluster singles and doubles with perturbative triples corrections: CCSD(T)-F12, J. Chem. Phys., 148, 114104, https://doi.org/10.1063/1.5020436, 2018.
Hoesly, R. M., Smith, S. J., Feng, L., Klimont, Z., Janssens-Maenhout, G., Pitkanen, T., Seibert, J. J., Vu, L., Andres, R. J., Bolt, R. M., Bond, T. C., Dawidowski, L., Kholod, N., Kurokawa, J.-I., Li, M., Liu, L., Lu, Z., Moura, M. C. P., O'Rourke, P. R., and Zhang, Q.: Historical (1750–2014) anthropogenic emissions of reactive gases and aerosols from the Community Emissions Data System (CEDS), Geosci. Model Dev., 11, 369–408, https://doi.org/10.5194/gmd-11-369-2018, 2018.
Hu, R., Zhang, G., Cai, H., Guo, J., Lu, K., Li, X., Lou, S., Tan, Z., Hu, C., Xie, P., and Liu, W.: Accurate elucidation of oxidation under heavy ozone pollution: a full suite of radical measurements in the chemically complex atmosphere, Atmos. Chem. Phys., 25, 3011–3028, https://doi.org/10.5194/acp-25-3011-2025, 2025.
Jalan, A., Allen, J. W., and Green, W. H.: Chemically activated formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones, Phys. Chem. Chem. Phys., 15, 16841–16852, https://doi.org/10.1039/C3CP52598H, 2013.
Jenkin, M. E., Valorso, R., Aumont, B., Rickard, A. R., and Wallington, T. J.: Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction, Atmos. Chem. Phys., 18, 9329–9349, https://doi.org/10.5194/acp-18-9329-2018, 2018.
Jiang, H., Liu, Y., Xiao, C., Yang, X., and Dong, W.: Reaction Kinetics of CH2OO and syn-CH3CHOO Criegee Intermediates with Acetaldehyde, J. Phys. Chem. A, 128, 4956–4965, https://doi.org/10.1021/acs.jpca.4c01374, 2024.
Jiménez, E., Lanza, B., Martínez, E., and Albaladejo, J.: Daytime tropospheric loss of hexanal and trans-2-hexenal: OH kinetics and UV photolysis, Atmos. Chem. Phys., 7, 1565–1574, https://doi.org/10.5194/acp-7-1565-2007, 2007.
Kaipara, R. and Rajakumar, B.: Temperature-dependent kinetics of the reaction of a Criegee intermediate with propionaldehyde: A computational investigation, J. Phys. Chem. A, 122, 8433–8445, https://doi.org/10.1021/acs.jpca.8b06603, 2018.
Kállay, M., Nagy, P. R., Mester, D., Rolik, Z., Samu, G., Csontos, J., Csóka, J., Szabó, P. B., Gyevi-Nagy, L., Hégely, B., Ladjánszki, I., Szegedy, L., Ladóczki, B., Petrov, K., Farkas, M., Mezei, P. D., and Ganyecz, Á.: The MRCC program system: Accurate quantum chemistry from water to proteins, J. Chem. Phys., 152, 074107, https://doi.org/10.1063/1.5142048, 2020.
Khan, M. A. H., Percival, C. J., Caravan, R. L., Taatjes, C. A., and Shallcross, D. E.: Criegee intermediates and their impacts on the troposphere, Environ. Sci. Processes Impacts, 20, 437–453, https://doi.org/10.1039/C7EM00585G, 2018.
Klippenstein, S. J.: RRKM theory and its implementation, in: Comprehensive Chemical Kinetics, Elsevier, 55–103, https://doi.org/10.1016/S0069-8040(03)80004-3, 2003.
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.
Knote, C., Hodzic, A., Jimenez, J. L., Volkamer, R., Orlando, J. J., Baidar, S., Brioude, J., Fast, J., Gentner, D. R., Goldstein, A. H., Hayes, P. L., Knighton, W. B., Oetjen, H., Setyan, A., Stark, H., Thalman, R., Tyndall, G., Washenfelder, R., Waxman, E., and Zhang, Q.: Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model, Atmos. Chem. Phys., 14, 6213–6239, https://doi.org/10.5194/acp-14-6213-2014, 2014.
Komazaki, Y., Hiratsuka, M., Narita, Y., Tanaka, S., and Fujita, T.: The development of an automated continuous measurement system for the monitoring of HCHO and CH3CHO in the atmosphere by using an annular diffusion scrubber coupled to HPLC, Fresen. J. Anal. Chem., 363, 686–695, https://doi.org/10.1007/s002160051272, 1999.
Kukui, A., Chartier, M., Wang, J., Chen, H., Dusanter, S., Sauvage, S., Michoud, V., Locoge, N., Gros, V., Bourrianne, T., Sellegri, K., and Pichon, J.-M.: Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions, Atmos. Chem. Phys., 21, 13333–13351, https://doi.org/10.5194/acp-21-13333-2021, 2021.
Lary, D. J. and Shallcross, D. E.: Central role of carbonyl compounds in atmospheric chemistry, J. Geophys. Res.-Atmos., 105, 19771–19778, https://doi.org/10.1029/1999JD901184, 2000.
Lelieveld, J., Gromov, S., Pozzer, A., and Taraborrelli, D.: Global tropospheric hydroxyl distribution, budget and reactivity, Atmos. Chem. Phys., 16, 12477–12493, https://doi.org/10.5194/acp-16-12477-2016, 2016.
Li, F., Tang, S., Lv, J., Yu, S., Sun, X., Cao, D., Wang, Y., and Jiang, G.: Critical contribution of chemically diverse carbonyl molecules to the oxidative potential of atmospheric aerosols, Atmos. Chem. Phys., 24, 8397–8411, https://doi.org/10.5194/acp-24-8397-2024, 2024.
Lily, M., Hynniewta, S., Muthiah, B., Wang, W., Chandra, A. K., and Liu, F.: Quantum chemical insights into the atmospheric reactions of CH2FCH2OH with OH radical, fate of CH2FC•HOH radical and ozone formation potential, Atmos. Environ., 249, 118247, https://doi.org/10.1016/j.atmosenv.2021.118247, 2021.
Lin, H., Jacob, D. J., Lundgren, E. W., Sulprizio, M. P., Keller, C. A., Fritz, T. M., Eastham, S. D., Emmons, L. K., Campbell, P. C., Baker, B., Saylor, R. D., and Montuoro, R.: Harmonized Emissions Component (HEMCO) 3.0 as a versatile emissions component for atmospheric models: application in the GEOS-Chem, NASA GEOS, WRF-GC, CESM2, NOAA GEFS-Aerosol, and NOAA UFS models, Geosci. Model Dev., 14, 5487–5506, https://doi.org/10.5194/gmd-14-5487-2021, 2021.
Liu, Q., Gao, Y., Huang, W., Ling, Z., Wang, Z., and Wang, X.: Carbonyl compounds in the atmosphere: A review of abundance, source and their contributions to O3 and SOA formation, Atmos. Res., 274, 106184, https://doi.org/10.1016/j.atmosres.2022.106184, 2022.
Liu, S., Chen, Y., Jiang, H., Shi, J., Ding, H., Yang, X., and Dong, W.: Reaction between Criegee Intermediate CH2OO and Isobutyraldehyde: Kinetics and Atmospheric Implications, Chem. Select, 8, e202303129, https://doi.org/10.1002/slct.202303129, 2023.
Liu, Y., Zhou, X., Chen, Y., Chen, M., Xiao, C., Dong, W., and Yang, X.: Temperature- and pressure-dependent rate coefficient measurement for the reaction of CH2OO with CH3CH2CHO, Phys. Chem. Chem. Phys., 22, 25869–25875, https://doi.org/10.1039/D0CP04316H, 2020.
Long, B., Bao, J. L., and Truhlar, D. G.: Atmospheric chemistry of Criegee intermediates: unimolecular reactions and reactions with water, J. Am. Chem. Soc., 138, 14409–14422, https://doi.org/10.1021/jacs.6b08655, 2016.
Long, B., Bao, J. L., and Truhlar, D. G.: Kinetics of the strongly correlated CH3O + O2 reaction: The importance of quadruple excitations in atmospheric and combustion chemistry, J. Am. Chem. Soc., 141, 611–617, https://doi.org/10.1021/jacs.8b11766, 2019.
Long, B., Wang, Y., Xia, Y., He, X., Bao, J. L., and Truhlar, D. G.: Atmospheric kinetics: Bimolecular reactions of carbonyl oxide by a triple-level strategy, J. Am. Chem. Soc., 143, 8402–8413, https://doi.org/10.1021/jacs.1c02029, 2021.
Long, B., Xia, Y., and Truhlar, D. G.: Quantitative kinetics of HO2 reactions with aldehydes in the atmosphere: High-order dynamic correlation, anharmonicity, and falloff effects are all important, J. Am. Chem. Soc., 144, 19910–19920, https://doi.org/10.1021/jacs.2c07994, 2022.
Long, B., Xia, Y., Zhang, Y.-Q., and Truhlar, D. G.: Kinetics of sulfur trioxide reaction with water vapor to form atmospheric sulfuric acid, J. Am. Chem. Soc., 145, 19866–19876, https://doi.org/10.1021/jacs.3c06032, 2023.
Long, B., Zhang, Y.-Q., Xie, C.-L., Tan, X.-F., and Truhlar, D. G.: Reaction of carbonyl oxide with hydroperoxymethyl thioformate: Quantitative kinetics and atmospheric implications, Research, 7, 0525, https://doi.org/10.34133/research.0525, 2024.
Long, B., Xie, C., and Truhlar, D. G.: Criegee intermediates compete well with OH as a cleaning agent for atmospheric amides, J. Am. Chem. Soc., 147, 22237–22244, https://doi.org/10.1021/jacs.5c07439, 2025.
Luecken, D. J., Hutzell, W. T., Strum, M. L., and Pouliot, G. A.: Regional sources of atmospheric formaldehyde and acetaldehyde, and implications for atmospheric modeling, Atmos. Environ., 47, 477–490, https://doi.org/10.1016/j.atmosenv.2011.10.005, 2012.
Luo, P.-L., Chen, I. Y., Khan, M. A. H., and Shallcross, D. E.: Direct gas-phase formation of formic acid through reaction of Criegee intermediates with formaldehyde, Commun. Chem., 6, 130, https://doi.org/10.1038/s42004-023-00933-2, 2023.
Lynch, B. J., Zhao, Y., and Truhlar, D. G.: Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory, J. Phys. Chem. A, 107, 1384–1388, https://doi.org/10.1021/jp021590l, 2003.
Manonmani, G., Sandhiya, L., and Senthilkumar, K.: Reaction of Criegee Intermediates with SO2-A Possible Route for Sulfurous Acid Formation in the Atmosphere, ACS Earth Space Chem., 7, 1890–1904, https://doi.org/10.1021/acsearthspacechem.3c00058, 2023.
Mellouki, A., Wallington, T. J., and Chen, J.: Atmospheric chemistry of oxygenated volatile organic compounds: Impacts on air quality and climate, Chem. Rev., 115, 3984–4014, https://doi.org/10.1021/cr500549n, 2015.
Novelli, A., Vereecken, L., Lelieveld, J., and Harder, H.: Direct observation of OH formation from stabilised Criegee intermediates, Phys. Chem. Chem. Phys., 16, 19941–19951, https://doi.org/10.1039/C4CP02719A, 2014.
Novelli, A., Hens, K., Tatum Ernest, C., Martinez, M., Nölscher, A. C., Sinha, V., Paasonen, P., Petäjä, T., Sipilä, M., Elste, T., Plass-Dülmer, C., Phillips, G. J., Kubistin, D., Williams, J., Vereecken, L., Lelieveld, J., and Harder, H.: Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument, Atmos. Chem. Phys., 17, 7807–7826, https://doi.org/10.5194/acp-17-7807-2017, 2017.
Papagni, C., Arey, J., and Atkinson, R.: Rate constants for the gas-phase reactions of a series of C3-C6 aldehydes with OH and NO3 radicals, Int. J. Chem. Kinet., 32, 79–84, https://doi.org/10.1002/(SICI)1097-4601(2000)32:2<79::AID-KIN2>3.0.CO;2-A, 2000.
Parker, T. M., Burns, L. A., Parrish, R. M., Ryno, A. G., and Sherrill, C. D.: Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies, J. Chem. Phys., 140, 094106, https://doi.org/10.1063/1.4867135, 2014.
Parrish, D. D., Ryerson, T. B., Mellqvist, J., Johansson, J., Fried, A., Richter, D., Walega, J. G., Washenfelder, R. A., de Gouw, J. A., Peischl, J., Aikin, K. C., McKeen, S. A., Frost, G. J., Fehsenfeld, F. C., and Herndon, S. C.: Primary and secondary sources of formaldehyde in urban atmospheres: Houston Texas region, Atmos. Chem. Phys., 12, 3273–3288, https://doi.org/10.5194/acp-12-3273-2012, 2012.
Peltola, J., Seal, P., Inkilä, A., and Eskola, A.: Time-resolved, broadband UV-absorption spectrometry measurements of Criegee intermediate kinetics using a new photolytic precursor: unimolecular decomposition of CH2OO and its reaction with formic acid, Phys. Chem. Chem. Phys., 22, 11797–11808, https://doi.org/10.1039/D0CP00302F, 2020.
Percival, C. J., Welz, O., Eskola, A. J., Savee, J. D., Osborn, D. L., Topping, D. O., Lowe, D., Utembe, S. R., Bacak, A., McFiggans, G., Cooke, M. C., Xiao, P., Archibald, A. T., Jenkin, M. E., Derwent, R. G., Riipinen, I., Mok, D. W. K., Lee, E. P. F., Dyke, J. M., Taatjes, C. A., and Shallcross, D. E.: Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation, Faraday Discuss., 165, 45–73, https://doi.org/10.1039/C3FD00048F, 2013.
Peverati, R. and Truhlar, D. G.: M11-L: A Local Density Functional That Provides Improved Accuracy for Electronic Structure Calculations in Chemistry and Physics, J. Phys. Chem. Lett., 3, 117–124, https://doi.org/10.1021/jz201525m, 2012.
Raghunath, P., Lee, Y.-P., and Lin, M. C.: Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO, J. Phys. Chem. A, 121, 3871–3878, https://doi.org/10.1021/acs.jpca.7b02196, 2017.
Ren, X., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Shirley, T., Adams, J., Simpas, J. B., and Brune, W. H.: HOx concentrations and OH reactivity observations in New York City during PMTACS-NY2001, Atmos. Environ., 37, 3627–3637, https://doi.org/10.1016/S1352-2310(03)00460-6, 2003.
Scollard, D. J., Treacy, J. J., Sidebottom, H. W., Balestra-Garcia, C., Laverdet, G., LeBras, G., MacLeod, H., and Teton, S.: Rate constants for the reactions of hydroxyl radicals and chlorine atoms with halogenated aldehydes, J. Phys. Chem., 97, 4683–4688, https://doi.org/10.1021/j100120a021, 1993.
Sellevåg, S. R., Stenstrøm, Y., Helgaker, T., and Nielsen, C. J.: Atmospheric chemistry of CHF2CHO: Study of the IR and UV−Vis absorption cross sections, photolysis, and OH-, Cl-, and NO3-Initiated oxidation, J. Phys. Chem. A, 109, 3652–3662, https://doi.org/10.1021/jp050313m, 2005.
Sivakumaran, V., Hölscher, D., Dillon, T. J., and Crowley, J. N.: Reaction between OH and HCHO: temperature dependent rate coefficients (202–399 K) and product pathways (298 K), Phys. Chem. Chem. Phys., 5, 4821–4827, https://doi.org/10.1039/B306859E, 2003.
Stone, D., Whalley, L. K., and Heard, D. E.: Tropospheric OH and HO2 radicals: field measurements and model comparisons, Chem. Soc. Rev., 41, 6348–6404, https://doi.org/10.1039/C2CS35140D, 2012.
Stone, D., Blitz, M., Daubney, L., Howes, N. U. M., and Seakins, P.: Kinetics of CH2OO reactions with SO2, NO2, NO, H2O and CH3CHO as a function of pressure, Phys. Chem. Chem. Phys., 16, 1139–1149, https://doi.org/10.1039/C3CP54391A, 2014.
Sun, Y., Long, B., and Truhlar, D. G.: Unimolecular Reactions of E-Glycolaldehyde Oxide and Its Reactions with One and Two Water Molecules, Research, 6, 0143, https://doi.org/10.34133/research.0143, 2024.
Taatjes, C. A., Welz, O., Eskola, A. J., Savee, J. D., Osborn, D. L., Lee, E. P. F., Dyke, J. M., Mok, D. W. K., Shallcross, D. E., and Percival, C. J.: Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone, Phys. Chem. Chem. Phys., 14, 10391–10400, https://doi.org/10.1039/C2CP40294G, 2012.
Tereszchuk, K. A. and Bernath, P. F.: Infrared absorption cross-sections for acetaldehyde (CH3CHO) in the 3µm region, J. Quant. Spectrosc. Radiat. Transfer, 112, 990–993, https://doi.org/10.1016/j.jqsrt.2010.12.003, 2011.
Thévenet, R., Mellouki, A., and Le Bras, G.: Kinetics of OH and Cl reactions with a series of aldehydes, Int. J. Chem. Kinet., 32, 676–685, https://doi.org/10.1002/1097-4601(2000)32:11<676::AID-KIN3>3.0.CO;2-V, 2000.
Wang, P.-B., Truhlar, D. G., Xia, Y., and Long, B.: Temperature-dependent kinetics of the atmospheric reaction between CH2OO and acetone, Phys. Chem. Chem. Phys., 24, 13066–13073, https://doi.org/10.1039/D2CP01118B, 2022.
Wei, Y., Zhang, Q., Huo, X., Wang, W., and Wang, Q.: The reaction of Criegee intermediates with formamide and its implication to atmospheric aerosols, Chemosphere, 296, 133717, https://doi.org/10.1016/j.chemosphere.2022.133717, 2022.
Wenger, J. C.: Chamber Studies on the Photolysis of Aldehydes Environmental, Environmental Simulation Chambers: Application to Atmospheric Chemical Processes, Dordrecht, 111–119, https://doi.org/10.1007/1-4020-4232-9_8,, 2006.
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., and Welborn, M.: MOLPRO, version 2019.2, a package of ab initio programs, https://www.molpro.net/ (last access: 4 November 2025), 2019.
Xia, Y., Long, B., Lin, S., Teng, C., Bao, J. L., and Truhlar, D. G.: Large pressure effects caused by internal rotation in the s-cis-syn-Acrolein stabilized Criegee intermediate at tropospheric temperature and pressure, J. Am. Chem. Soc., 144, 4828–4838, https://doi.org/10.1021/jacs.1c12324, 2022.
Xia, Y., Long, B., Liu, A., and Truhlar, D. G.: Reactions with Criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere, Fundam. Res., 4, 1216–1224, https://doi.org/10.1016/j.fmre.2023.02.012, 2024.
Xia, Y., Zhang, W., Tang, X., and Long, B.: Quantitative kinetics of the hydrogen shift reaction of methylthiomethyl peroxy radical (CH3SCH2OO) in the atmosphere, J. Phys. Chem. A, 129, 2275–2285, https://doi.org/10.1021/acs.jpca.4c06818, 2025.
Yang, X., Xue, L., Wang, T., Wang, X., Gao, J., Lee, S., Blake, D. R., Chai, F., and Wang, W.: Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species, J. Geophys. Res.-Atmos., 123, 1426–1440, https://doi.org/10.1002/2017JD027403, 2018.
Zhang, L., Truhlar, D. G., and Sun, S.: Association of Cl with C2H2 by unified variable-reaction-coordinate and reaction-path variational transition-state theory, Proc. Natl. Acad. Sci., 117, 5610–5616, https://doi.org/10.1073/pnas.1920018117, 2020.
Zhang, R. M., Xu, X., and Truhlar, D. G.: TUMME: Tsinghua University Minnesota Master Equation program, Comput. Phys. Commun., 270, 108140, https://doi.org/10.1016/j.cpc.2021.108140, 2022.
Zhang, T., Wen, M., Ding, C., Zhang, Y., Ma, X., Wang, Z., Lily, M., Liu, J., and Wang, R.: Multiple evaluations of atmospheric behavior between Criegee intermediates and HCHO: Gas-phase and air-water interface reaction, J. Environ. Sci., 127, 308–319, https://doi.org/10.1016/j.jes.2022.06.004, 2023.
Zhang, Y., Mu, Y., Liu, J., and Mellouki, A.: Levels, sources and health risks of carbonyls and BTEX in the ambient air of Beijing, China, J. Environ. Sci., 24, 124–130, https://doi.org/10.1016/S1001-0742(11)60735-3, 2012.
Zhao, M., Shen, H., Zhang, J., Liu, Y., Sun, Y., Wang, X., Dong, C., Zhu, Y., Li, H., Shan, Y., Mu, J., Zhong, X., Tang, J., Guo, M., Wang, W., and Xue, L.: Carbonyl Compounds Regulate Atmospheric Oxidation Capacity and Particulate Sulfur Chemistry in the Coastal Atmosphere, Environ. Sci. Technol., 58, 17334–17343, https://doi.org/10.1021/acs.est.4c03947, 2024.
Zheng, J. and Truhlar, D. G.: Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions, Faraday Discuss., 157, 59–88, https://doi.org/10.1039/C2FD20012K, 2012.
Zheng, J., Zhang, S., and Truhlar, D. G.: Density Functional Study of Methyl Radical Association Kinetics, J. Phys. Chem. A, 112, 11509–11513, https://doi.org/10.1021/jp806617m, 2008.
Zheng, J., Mielke, S. L., Clarkson, K. L., and Truhlar, D. G.: MSTor: A program for calculating partition functions, free energies, enthalpies, entropies, and heat capacities of complex molecules including torsional anharmonicity, Comput. Phys. Commun., 183, 1803–1812, https://doi.org/10.1016/j.cpc.2012.03.007, 2012.
Zheng, J., Bao, J. L., Meana-Pañeda, R., Zhang, S., J.Lynch, B., Corchado, J. C., Chuang, Y., Fast, P. L., Hu, W.-P., Liu, Y.-P., Lynch, G. C., Nguyen, K. A., Jackels, C. F., Ramos, A. F., Ellingson, B. A., Melissas, V. S., Villà, J., Rossi, I., Coitiño, E. L., Pu, J., Albu, T. V., Ratkiewicz, A., Steckler, R., Garrett, B. C., Isaacson, A. D., and Truhlar, D. G.: Polyrate-version 2017-C; University of Minnesota: Minneapolis, https://comp.chem.umn.edu/polyrate/ (last access: 4 November 2025), 2017.
Zheng, J., Bao, J. L., Zhang, S., Corchado, J. C., Chuang, Y., Ellingson, B. A., and Truhlar, D. G.: Gaussrate, version 2017-B; University of Minnesota: Minneapolis, MN, https://comp.chem.umn.edu/polyrate/ (last access: 4 November 2025), 2018.
Zhu, L., Talukdar, R. K., Burkholder, J. B., and Ravishankara, A. R.: Rate coefficients for the OH + acetaldehyde (CH3CHO) reaction between 204 and 373 K, Int. J. Chem. Kinet., 40, 635–646, https://doi.org/10.1002/kin.20346, 2008.
Short summary
Chemical transformations are fundamental drivers of atmospheric composition. While elucidating these processes is critical, existing quantitative kinetic data remain significantly limited. We develop a computational framework that delivers quantitative kinetics for CH₂OO reactions with aldehydes from small to large systems, revealing fluorination-driven near–collision-limit reactivity and previously unrecognized impacts on nighttime Criegee chemistry and sulfate formation in the atmosphere.
Chemical transformations are fundamental drivers of atmospheric composition. While elucidating...
Altmetrics
Final-revised paper
Preprint