Articles | Volume 25, issue 22
https://doi.org/10.5194/acp-25-16713-2025
© Author(s) 2025. 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-25-16713-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
25 Nov 2025
Research article |
| 25 Nov 2025
| 25 Nov 2025
Criegee + HONO reaction: a bimolecular sink of Criegee, and the missing non-photolytic source of OH•
Vishva Jeet Anand
Department of Chemistry, Malaviya National Institute of Technology Jaipur, Jaipur, 302017, India
Philips Kumar Rai
Department of Chemistry, Malaviya National Institute of Technology Jaipur, Jaipur, 302017, India
Department of Chemistry, Malaviya National Institute of Technology Jaipur, Jaipur, 302017, India
Cited articles
Acker, K., Möller, D., Wieprecht, W., Meixner, F. X., Bohn, B., Gilge, S., Plass-Dülmer, C., and Berresheim, H.: Strong daytime production of OH from HNO2 at a rural mountain site, Geophys. Res. Lett., 33, L02809, https://doi.org/10.1029/2005GL024643, 2006. a
Alam, M. S., Camredon, M., Rickard, A. R., Carr, T., Wyche, K. P., Hornsby, K. E., Monks, P. S., and Bloss, W. J.: Total radical yields from tropospheric ethene ozonolysis, Phys. Chem. Chem. Phys., 13, 11002–11015, 2011. a
Alicke, B., Geyer, A., Hofzumahaus, A., Holland, F., Konrad, S., Pätz, H., Schäfer, J., Stutz, J., Volz-Thomas, A., and Platt, U.: OH formation by HONO photolysis during the BERLIOZ experiment, J. Geophys. Res., 108, https://doi.org/10.1029/2001JD000579, 2003. a
Anand, V. J. and Kumar, P.: Mechanistic insight into the N2O + O(1D, 3P) reaction: role of post-CCSD (T) corrections and non-adiabatic effects, Phys. Chem. Chem. Phys., 25, 33119–33129, 2023. a
Anderson, J. G.: Free Radicals in the Earth's Atmosphere: Their Measurement and Interpretation, Annu. Rev. Phys. Chem., 38, 489–520, 1987. a
Anglada, J. M. and Sole, A.: The atmospheric oxidation of HONO by OH, Cl, and ClO radicals, J. Phys. Chem. A, 121, 9698–9707, 2017. a
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. a
Aumont, B., Chervier, F., and Laval, S.: Contribution of HONO sources to the NOX/HOX/O3 chemistry in the polluted boundary layer, Atmos. Environ., 37, 487–498, 2003. a
Barker, J., Nguyen, T., Stanton, J., Aieta, C., Ceotto, M., Gabas, F., Kumar, T., Li, C., Lohr, L., Maranzana, A., Ortiz, N., Preses, J., Simmie, J., Sonk, J., and Stimac, P.: MultiWell-2021 Software Suite; J. R. Barker, University of Michigan, Ann Arbor, Michigan, USA, https://multiwell.engin.umich.edu/ (last access: 5 March 2025), 2021. a
Berndt, T., Hyttinen, N., Herrmann, H., and Hansel, A.: First oxidation products from the reaction of hydroxyl radicals with isoprene for pristine environmental conditions, Commun. Chem., 2, 21, https://doi.org/10.1038/s42004-019-0120-9, 2019. a
Bottorff, B., Lew, M. M., Woo, Y., Rickly, P., Rollings, M. D., Deming, B., Anderson, D. C., Wood, E., Alwe, H. D., Millet, D. B., Weinheimer, A., Tyndall, G., Ortega, J., Dusanter, S., Leonardis, T., Flynn, J., Erickson, M., Alvarez, S., Rivera-Rios, J. C., Shutter, J. D., Keutsch, F., Helmig, D., Wang, W., Allen, H. M., Slade, J. H., Shepson, P. B., Bertman, S., and Stevens, P. S.: OH, HO2, and RO2 radical chemistry in a rural forest environment: measurements, model comparisons, and evidence of a missing radical sink, Atmos. Chem. Phys., 23, 10287–10311, https://doi.org/10.5194/acp-23-10287-2023, 2023. a
Buszek, R. J., Barker, J. R., and Francisco, J. S.: Water effect on the OH + HCl reaction, J. Phys. Chem. A, 116, 4712–4719, 2012. a
Calvert, J., Yarwood, G., and Dunker, A.: An evaluation of the mechanism of nitrous acid formation in the urban atmosphere, Res. Chem. Intermed., 20, 463–502, 1994. a
Carslaw, N., Creasey, D., Harrison, D., Heard, D., Hunter, M., Jacobs, P., Jenkin, M., Lee, J., Lewis, A., Pilling, M., Saunders, S., and Seakins, P.: OH and HO2 radical chemistry in a forested region of north-western Greece, Atmos. Environ., 35, 4725–4737, 2001. a
Cox, R. A., Ammann, M., Crowley, J. N., Herrmann, H., Jenkin, M. E., McNeill, V. F., Mellouki, A., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates, Atmos. Chem. Phys., 20, 13497–13519, https://doi.org/10.5194/acp-20-13497-2020, 2020. a
Criegee, R.: Mechanism of ozonolysis, Angew. Chem. Internat. Edit., 14, 745–752, 1975. a
Crounse, J. D., Paulot, F., Kjaergaard, H. G., and Wennberg, P. O.: Peroxy radical isomerization in the oxidation of isoprene, Phys. Chem. Chem. Phys., 13, 13607–13613, 2011. a
Donahue, N. M., Drozd, G. T., Epstein, S. A., Presto, A. A., and Kroll, J. H.: Adventures in ozoneland: down the rabbit-hole, Phys. Chem. Chem. Phys., 13, 10848–10857, 2011. a
Ehhalt, D.: Free Radicals in the Atmosphere, Free Radic. Res. Commun., 3, 153–164, 1987. a
Faloona, I., Tan, D., Brune, W., Hurst, J., Barket Jr., D., Couch, T. L., Shepson, P., Apel, E., Riemer, D., Thornberry, T., Carroll, M. A., Sillman, S., Keeler, G. J., Sagady, J., Hooper, D., and Paterson, K.: Nighttime observations of anomalously high levels of hydroxyl radicals above a deciduous forest canopy, J. Geophys. Res. Atmos., 106, 24315–24333, 2001. a
Fang, Y., Barber, V. P., Klippenstein, S. J., McCoy, A. B., and Lester, M. I.: Tunneling Effects in the Unimolecular Decay of (CH3)2COO Criegee Intermediates to OH Radical Products, J. Chem. Phys., 146, 134307, https://doi.org/10.1063/1.4979297, 2017. a
Feiner, P. A., Brune, W. H., Miller, D. O., Zhang, L., Cohen, R. C., Romer, P. S., Goldstein, A. H., Keutsch, F. N., Skog, K. M., Wennberg, P. O., Nguyen, T. B., Teng, A. P., DeGouw, J., Koss, A., Wild, R. J., Brown, S. S., Guenther, A., Edgerton, E., Baumann, K., and Fry, J. L.: Testing atmospheric oxidation in an Alabama forest, J. Atmos. Sci., 73, 4699–4710, 2016. a
Fernández-Ramos, A., Miller, J. A., Klippenstein, S. J., and Truhlar, D. G.: Modeling the kinetics of bimolecular reactions, Chem. Rev., 106, 4518–4584, 2006. a
Geyer, A., Bächmann, K., Hofzumahaus, A., Holland, F., Konrad, S., Klüpfel, T., Pätz, H.-W., Perner, D., Mihelcic, D., Schäfer, H.-J., Volz-Thomas, A., and Platt, U.: Nighttime formation of peroxy and hydroxyl radicals during the BERLIOZ campaign: Observations and modeling studies, J. Geophys. Res. Atmos., 108, https://doi.org/10.1029/2001JD000656, 2003. a, b
Griffith, S. M., Hansen, R. F., Dusanter, S., Michoud, V., Gilman, J. B., Kuster, W. C., Veres, P. R., Graus, M., de Gouw, J. A., Roberts, J., Young, C., Washenfelder, R., Brown, S. S., Thalman, R., Waxman, E., Volkamer, R., Tsai, C., Stutz, J., Flynn, J. H., Grossberg, N., Lefer, B., Alvarez, S. L., Rappenglueck, B., Mielke, L. H., Osthoff, H. D., and Stevens, P. S.: Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets, J. Geophys. Res., 121, 4211–4232, 2016. a
Hall, I. W., Wayne, R. P., Cox, R. A., Jenkin, M. E., and Hayman, G. D.: Kinetics of the reaction of nitrate radical with hydroperoxo, J. Phys. Chem., 92, 5049–5054, 1988. a
Harrison, R., Yin, J., Tilling, R., Cai, X., Seakins, P., Hopkins, J., Lansley, D., Lewis, A., Hunter, M., Heard, D., Carpenter, L., Creasey, D., Lee, J., Pilling, M., Carslaw, N., Emmerson, K., Redington, A., Derwent, R., Ryall, D., Mills, G., and Penkett, S.: Measurement and modelling of air pollution and atmospheric chemistry in the UK West Midlands conurbation: Overview of the PUMA Consortium project, Sci. Total Environ., 360, 5–25, 2006. a
He, Y., Zhou, X., Hou, J., Gao, H., and Bertman, S. B.: Importance of dew in controlling the air-surface exchange of HONO in rural forested environments, Geophys. Res. Lett., 33, L02813, https://doi.org/10.1029/2005GL024348, 2006. a
Heald, C. L. and Kroll, J. H.: A radical shift in air pollution, Science, 374, 688–689, 2021. a
Heard, D., Carpenter, L., Creasey, D., Hopkins, J., Lee, J., Lewis, A., Pilling, M., Seakins, P., Carslaw, N., and Emmerson, K.: High levels of the hydroxyl radical in the winter urban troposphere, Geophys. Res. Lett., 31, L18112, https://doi.org/10.1029/2004GL020544, 2004. a
Hens, K., Novelli, A., Martinez, M., Auld, J., Axinte, R., Bohn, B., Fischer, H., Keronen, P., Kubistin, D., Nölscher, A. C., Oswald, R., Paasonen, P., Petäjä, T., Regelin, E., Sander, R., Sinha, V., Sipilä, M., Taraborrelli, D., Tatum Ernest, C., Williams, J., Lelieveld, J., and Harder, H.: Observation and modelling of HOx radicals in a boreal forest, Atmos. Chem. Phys., 14, 8723–8747, https://doi.org/10.5194/acp-14-8723-2014, 2014. a, b
Horie, O. and Moortgat, G.: Decomposition pathways of the excited Criegee intermediates in the ozonolysis of simple alkenes, Atmos. Environ., 25A, 1881–1896, 1991. a
Medeiros, D. J., Blitz, M. A., Seakins, P. W., and Whalley, L. K.: Direct measurements of isoprene autoxidation: Pinpointing atmospheric oxidation in tropical forests, JACS Au, 2, 809–818, 2022. a
Johnson, D. and Marston, G.: The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere, Chem. Soc. Rev., 37, 699–716, 2008. a
Kim, S., Kim, S.-Y., Lee, M., Shim, H., Wolfe, G. M., Guenther, A. B., He, A., Hong, Y., and Han, J.: Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest, Atmos. Chem. Phys., 15, 4357–4371, https://doi.org/10.5194/acp-15-4357-2015, 2015. a
Lelieveld, J., Peters, W., Dentener, F., and Krol, M.: Stability of tropospheric hydroxyl chemistry, J. Geophys. Res., 107, https://doi.org/10.1029/2002JD002272, 2002. a
Lelieveld, J., Dentener, F. J., Peters, W., and Krol, M. C.: On the role of hydroxyl radicals in the self-cleansing capacity of the troposphere, Atmos. Chem. Phys., 4, 2337–2344, https://doi.org/10.5194/acp-4-2337-2004, 2004. a
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. a
Lelieveld, J. a., Butler, T. M., Crowley, J. N., Dillon, T. J., Fischer, H., Ganzeveld, L., Harder, H., Lawrence, M. G., Martinez, M., Taraborrelli, D., and Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest, Nature, 452, 737–740, 2008. a
Lew, M. M., Rickly, P. S., Bottorff, B. P., Reidy, E., Sklaveniti, S., Léonardis, T., Locoge, N., Dusanter, S., Kundu, S., Wood, E., and Stevens, P. S.: OH and HO2 radical chemistry in a midlatitude forest: measurements and model comparisons, Atmos. Chem. Phys., 20, 9209–9230, https://doi.org/10.5194/acp-20-9209-2020, 2020. a
Li, Y., Wang, X., Wu, Z., Li, L., Wang, C., Li, H., Zhang, X., Zhang, Y., Li, J., Gao, R., Xue, L., Mellouki, A., Ren, Y., and Zhang, Q.: Atmospheric nitrous acid (HONO) in an alternate process of haze pollution and ozone pollution in urban Beijing in summertime: Variations, sources and contribution to atmospheric photochemistry, Atmos. Res., 260, 105689, https://doi.org/10.1016/j.atmosres.2021.105689, 2021. a
Lin, H.-Y., Huang, Y.-H., Wang, X., Bowman, J. M., Nishimura, Y., Witek, H. A., and Lee, Y.-P.: Infrared identification of the Criegee intermediates syn-and anti-CH3CHOO, and their distinct conformation-dependent reactivity, Nat. Commun., 6, 7012, https://doi.org/10.1038/ncomms8012, 2015. a
Lin, L.-C., Chang, H.-T., Chang, C.-H., Chao, W., Smith, M. C., Chang, C.-H., Jr-Min Lin, J., and Takahashi, K.: Competition between H2O and (H2O)2 reactions with CH2OO/CH3CHOO, Phys. Chem. Chem. Phys., 18, 4557–4568, 2016. a
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, 2016. a
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, 2021. a
Lu, K. D., Rohrer, F., Holland, F., Fuchs, H., Bohn, B., Brauers, T., Chang, C. C., Häseler, R., Hu, M., Kita, K., Kondo, Y., Li, X., Lou, S. R., Nehr, S., Shao, M., Zeng, L. M., Wahner, A., Zhang, Y. H., and Hofzumahaus, A.: Observation and modelling of OH and HO2 concentrations in the Pearl River Delta 2006: a missing OH source in a VOC rich atmosphere, Atmos. Chem. Phys., 12, 1541–1569, https://doi.org/10.5194/acp-12-1541-2012, 2012. a
Lu, X., Park, J., and Lin, M.-C.: Gas phase reactions of HONO with NO2, O3, and HCl: Ab initio and TST study, J. Phys. Chem. A, 104, 8730–8738, 2000. a
Mallick, S. and Kumar, P.: Impact of Post-CCSD(T) Corrections on Reaction Energetics and Rate Constants of the OH• + HCl Reaction, J. Phys. Chem. A, 122, 7151–7159, 2018. a
Mallick, S. and Kumar, P.: The reaction of N2O with the Criegee intermediate: A theoretical study, Comput. Theor. Chem., 1191, 113023, https://doi.org/10.1016/j.comptc.2020.113023, 2020. a
Mallick, S., Kumar, A., and Kumar, P.: Revisiting the reaction energetics of the CH3O• + O2 (3Σ−) reaction: the crucial role of post-CCSD(T) corrections, Phys. Chem. Chem. Phys., 21, 6559–6565, 2019. a
Mellouki, A., Le Bras, G., and Poulet, G.: Kinetics of the reactions of nitrate radical with hydroxyl and hydroperoxo, J. Phys. Chem. A, 92, 2229–2234, 1988. a
Mellouki, A., Talukdar, R., Bopegedera, A., and Howard, C. J.: Study of the kinetics of the reactions of NO3 with HO2 and OH, Int. J. Chem. Kinet., 25, 25–39, 1993. a
Misiewicz, J. P., Elliott, S. N., Moore, K. B., and Schaefer, H. F.: Re-examining ammonia addition to the Criegee intermediate: converging to chemical accuracy, Phys. Chem. Chem. Phys., 20, 7479–7491, 2018. a
Monks, P. S.: Gas-phase radical chemistry in the troposphere, Chem. Soc. Rev., 34, 376–395, 2005. a
Nguyen, T. L., Li, J., Dawes, R., Stanton, J. F., and Guo, H.: Accurate determination of barrier height and kinetics for the F + H2
→ HF + OH reaction, J. Phys. Chem. A, 117, 8864–8872, 2013. a
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, 2014. a
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. a
Novelli, A., Vereecken, L., Bohn, B., Dorn, H.-P., Gkatzelis, G. I., Hofzumahaus, A., Holland, F., Reimer, D., Rohrer, F., Rosanka, S., Taraborrelli, D., Tillmann, R., Wegener, R., Yu, Z., Kiendler-Scharr, A., Wahner, A., and Fuchs, H.: Importance of isomerization reactions for OH radical regeneration from the photo-oxidation of isoprene investigated in the atmospheric simulation chamber SAPHIR, Atmos. Chem. Phys., 20, 3333–3355, https://doi.org/10.5194/acp-20-3333-2020, 2020. a
Onel, L., Lade, R., Mortiboy, J., Blitz, M. A., Seakins, P. W., Heard, D. E., and Stone, D.: Kinetics of the gas phase reaction of the Criegee intermediate CH2OO with SO2 as a function of temperature, Phys. Chem. Chem. Phys., 23, 19415–19423, 2021. a
Osborn, D. L. and Taatjes, C. A.: The physical chemistry of Criegee intermediates in the gas phase, Int. Rev. Phys. Chem., 34, 309–360, 2015. a
Pansini, F., Neto, A., and Varandas, A.: Extrapolation of Hartree–Fock and multiconfiguration self-consistent-field energies to the complete basis set limit, Theor. Chem. Acc., 135, 1–6, 2016. a
Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kürten, A., St. Clair, J. M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected epoxide formation in the gas-phase photooxidation of isoprene, Science, 325, 730–733, 2009. a
Peeters, J. and Müller, J.-F.: HOX radical regeneration in isoprene oxidation via peroxy radical isomerisations. II: experimental evidence and global impact, Phys. Chem. Chem. Phys., 12, 14227–14235, 2010. a
Peeters, J., Nguyen, T. L., and Vereecken, L.: HOX radical regeneration in the oxidation of isoprene, Phys. Chem. Chem. Phys., 11, 5935–5939, 2009. a
Prinn, R. G.: The Cleansing Capacity of the Atmosphere, Annu. Rev. Environ. Resour., 28, 29–57, 2003. a
Rai, P. K. and Kumar, P.: Role of post-CCSD (T) corrections in predicting the energetics and kinetics of the OH• + O3 reaction, Phys. Chem. Chem. Phys., 24, 13026–13032, 2022. a
Rai, P. K. and Kumar, P.: Accurate determination of reaction energetics and kinetics of HO
Reidy, E., Bottorff, B. P., Rosales, C. M. F., Cardoso-Saldaña, F. J., Arata, C., Zhou, S., Wang, C., Abeleira, A., Hildebrandt Ruiz, L., Goldstein, A. H., Novoselac, A., Kahan, T. F., Abbatt, J. P. D., Vance, M. E., Farmer, D. K., and Stevens, P. S.: Measurements of hydroxyl radical concentrations during indoor cooking events: Evidence of an unmeasured photolytic source of radicals, Environ. Sci. Technol., 57, 896–908, 2023. a
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, 2003. a
Ren, X., Brune, W. H., Oliger, A., Metcalf, A. R., Simpas, J. B., Shirley, T., Schwab, J. J., Bai, C., Roychowdhury, U., Li, Y., Cai, C., Demerjian, K. L., He, Y., Zhou, X., Gao, H., and Hou, J.: OH, HO2, and OH reactivity during the PMTACS–NY Whiteface Mountain 2002 campaign: Observations and model comparison, J. Geophys. Res. Atmos., 111, D10S03, https://doi.org/10.1029/2005JD006126, 2006. a
Ren, X., Gao, H., Zhou, X., Crounse, J. D., Wennberg, P. O., Browne, E. C., LaFranchi, B. W., Cohen, R. C., McKay, M., Goldstein, A. H., and Mao, J.: Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007, Atmos. Chem. Phys., 10, 6283–6294, https://doi.org/10.5194/acp-10-6283-2010, 2010. a
Rondon, A. and Sanhueza, E.: High HONO atmospheric concentrations during vegetation burning in the tropical savannah, Tellus B, 41, 474–477, 1989. a
Ruscic, B. and Bross, D. H.: Active Thermochemical Tables (ATcT) Thermochemical Values ver. 1.122v, https://doi.org/10.17038/CSE/1885921, 2021. a
Sander, R., Baumgaertner, A., Cabrera-Perez, D., Frank, F., Gromov, S., Grooß, J.-U., Harder, H., Huijnen, V., Jöckel, P., Karydis, V. A., Niemeyer, K. E., Pozzer, A., Riede, H., Schultz, M. G., Taraborrelli, D., and Tauer, S.: The community atmospheric chemistry box model CAABA/MECCA-4.0, Geosci. Model Dev., 12, 1365–1385, https://doi.org/10.5194/gmd-12-1365-2019, 2019. a
Shabin, M., Kumar, A., Hakkim, H., Rudich, Y., and Sinha, V.: Sources, sinks, and chemistry of stabilized Criegee intermediates in the indo-gangetic plain, Sci. Total Environ., 896, 165281, https://doi.org/10.1016/j.scitotenv.2023.165281, 2023. a
Sheps, L., Scully, A. M., and Au, K.: UV absorption probing of the conformer-dependent reactivity of a Criegee intermediate CH3CHOO, Phys. Chem. Chem. Phys., 16, 26701–26706, 2014. a
Slater, E. J., Whalley, L. K., Woodward-Massey, R., Ye, C., Lee, J. D., Squires, F., Hopkins, J. R., Dunmore, R. E., Shaw, M., Hamilton, J. F., Lewis, A. C., Crilley, L. R., Kramer, L., Bloss, W., Vu, T., Sun, Y., Xu, W., Yue, S., Ren, L., Acton, W. J. F., Hewitt, C. N., Wang, X., Fu, P., and Heard, D. E.: Elevated levels of OH observed in haze events during wintertime in central Beijing, Atmos. Chem. Phys., 20, 14847–14871, https://doi.org/10.5194/acp-20-14847-2020, 2020. a, b
Smith, M. C., Chao, W., Takahashi, K., Boering, K. A., and Lin, J. J.-M.: Unimolecular decomposition rate of the Criegee intermediate (CH3)2COO measured directly with UV absorption spectroscopy, J. Phys. Chem. A, 120, 4789–4798, 2016. a
Smith, S. C., Lee, J. D., Bloss, W. J., Johnson, G. P., Ingham, T., and Heard, D. E.: Concentrations of OH and HO2 radicals during NAMBLEX: measurements and steady state analysis, Atmos. Chem. Phys., 6, 1435–1453, https://doi.org/10.5194/acp-6-1435-2006, 2006. a
Song, M., Zhao, X., Liu, P., Mu, J., He, G., Zhang, C., Tong, S., Xue, C., Zhao, X., Ge, M., and Mu, Y.: Atmospheric NOX oxidation as major sources for nitrous acid (HONO), npj clim. atmos. sci., 6, 30, https://doi.org/10.1038/s41612-023-00357-8, 2023. a
Su, H., Cheng, Y. F., Shao, M., Gao, D. F., Yu, Z. Y., Zeng, L. M., Slanina, J., Zhang, Y. H., and Wiedensohler, A.: Nitrous acid (HONO) and its daytime sources at a rural site during the 2004 PRIDE-PRD experiment in China, J. Geophys. Res. Atmos., 113, D14312, https://doi.org/10.1029/2007JD009060, 2008. a
Taatjes, C. A.: Criegee intermediates: What direct production and detection can teach us about reactions of carbonyl oxides, Annu. Rev. Phys. Chem., 68, 183–207, 2017. a
Tajti, A., Szalay, P. G., Császár, A. G., Kállay, M., Gauss, J., Valeev, E. F., Flowers, B. A., Vázquez, J., and Stanton, J. F.: HEAT: High accuracy extrapolated ab initio thermochemistry, J. Chem. Phys., 121, 11599–11613, 2004. a
Tan, D., Faloona, I., Simpas, J. B., Brune, W., Shepson, P. B., Couch, T. L., Sumner, A. L., Carroll, M. A., Thornberry, T., Apel, E., Riemer, D., and Stockwell, W.: HOX budgets in a deciduous forest: Results from the PROPHET summer 1998 campaign, J. Geophys. Res. Atmos., 106, 24407–24427, 2001. a
Tan, Z., Fuchs, H., Lu, K., Hofzumahaus, A., Bohn, B., Broch, S., Dong, H., Gomm, S., Häseler, R., He, L., Holland, F., Li, X., Liu, Y., Lu, S., Rohrer, F., Shao, M., Wang, B., Wang, M., Wu, Y., Zeng, L., Zhang, Y., Wahner, A., and Zhang, Y.: Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO2 and RO2 radicals, Atmos. Chem. Phys., 17, 663–690, https://doi.org/10.5194/acp-17-663-2017, 2017. a
Teng, A. P., Crounse, J. D., and Wennberg, P. O.: Isoprene peroxy radical dynamics, J. Am. Chem. Soc., 139, 5367–5377, 2017. a
Varandas, A. and Pansini, F.: Narrowing the error in electron correlation calculations by basis set re-hierarchization and use of the unified singlet and triplet electron-pair extrapolation scheme: Application to a test set of 106 systems, J. Chem. Phys., 141, 224113, https://doi.org/10.1063/1.4903193, 2014. a
Vereecken, L.: The reaction of Criegee intermediates with acids and enols, Phys. Chem. Chem. Phys., 19, 28630–28640, 2017. a
Vereecken, L. and Francisco, J. S.: Theoretical studies of atmospheric reaction mechanisms in the troposphere, Chem. Soc. Rev., 41, 6259–6293, 2012. a
Vereecken, L., Harder, H., and Novelli, A.: The reactions of Criegee intermediates with alkenes, ozone, and carbonyl oxides, Phys. Chem. Chem. Phys., 16, 4039–4049, 2014. a
Vereecken, L., Rickard, A., Newland, M., and Bloss, W.: Theoretical study of the reactions of Criegee intermediates with ozone, alkylhydroperoxides, and carbon monoxide, Phys. Chem. Chem. Phys., 17, 23847–23858, 2015. a
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. a
Wallington, T. J. and Japar, S. M.: Fourier transform infrared kinetic studies of the reaction of HONO with HNO3, NO3 and N2O5 at 295 K, J. Atmos. Chem., 9, 399–409, 1989. a
Weinstock, B.: Carbon monoxide: Residence time in the atmosphere, Science, 166, 224–225, 1969. a
Whalley, L. K., Edwards, P. M., Furneaux, K. L., Goddard, A., Ingham, T., Evans, M. J., Stone, D., Hopkins, J. R., Jones, C. E., Karunaharan, A., Lee, J. D., Lewis, A. C., Monks, P. S., Moller, S. J., and Heard, D. E.: Quantifying the magnitude of a missing hydroxyl radical source in a tropical rainforest, Atmos. Chem. Phys., 11, 7223–7233, https://doi.org/10.5194/acp-11-7223-2011, 2011. a, b, c, d
Yang, X., Wang, H., Lu, K., Ma, X., Tan, Z., Long, B., Chen, X., Li, Y., Qu, K., Xia, Y., Zhang, Y., Li, X., Chen, S., Dong, H., Zeng, L., and Zhang, Y.: Reactive aldehyde chemistry explains the missing source of hydroxyl radicals, Nat. Commun., 15, 1648, https://doi.org/10.1038/s41467-024-45885-w, 2024. a, b
Zhang, N., Zhou, X., Bertman, S., Tang, D., Alaghmand, M., Shepson, P. B., and Carroll, M. A.: Measurements of ambient HONO concentrations and vertical HONO flux above a northern Michigan forest canopy, Atmos. Chem. Phys., 12, 8285–8296, https://doi.org/10.5194/acp-12-8285-2012, 2012. a, b
Zhou, X., Zhang, N., TerAvest, M., Tang, D., Hou, J., Bertman, S., Alaghmand, M., Shepson, P., Carroll, M., Griffith, S., Dusanter, S., and Stevens, P.: Nitric acid photolysis on forest canopy surface as a source for tropospheric nitrous acid, Nat. Geosci., 4, 440–443, https://doi.org/10.1038/ngeo1164, 2011. a
Østerstrøm, F. F., Carter, T. J., Shaw, D. R., Abbatt, J. P. D., Abeleira, A., Arata, C., Bottorff, B. P., Cardoso-Saldaña, F. J., DeCarlo, P. F., Farmer, D. K., Goldstein, A. H., Ruiz, L. H., Kahan, T. F., Mattila, J. M., Novoselac, A., Stevens, P. S., Reidy, E., Rosales, C. M. F., Wang, C., Zhou, S., and Carslaw, N.: Modelling indoor radical chemistry during the HOMEChem campaign, Environ. Sci.: Process. Impacts, 27, 188–201, https://doi.org/10.1039/D4EM00628C, 2025. a
Short summary
We have studied the energetics and kinetics of the bimolecular reaction of simple and dimethyl-substituted Criegee intermediates with HONO computationally. The investigation suggests that HONO can be an important sink for Criegee intermediates and a potential source of OH radicals. Our study also reveals that this reaction is also capable of recycling OH • ↔ HO•2 , and hence, can be key in resolving the discrepancy between observed and modeled concentrations of OH and HO2 radicals.
We have studied the energetics and kinetics of the bimolecular reaction of simple and...
Altmetrics
Final-revised paper
Preprint