Articles | Volume 25, issue 7
https://doi.org/10.5194/acp-25-4313-2025
© 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-25-4313-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
16 Apr 2025
Research article |
| 16 Apr 2025
| 16 Apr 2025
Monoterpene oxidation pathways initiated by acyl peroxy radical addition
Dominika Pasik
CORRESPONDING AUTHOR
Department of Chemistry, University of Helsinki, Helsinki, 00014, Finland
Institute for Atmospheric and Earth System Research, University of Helsinki, Helsinki, 00014, Finland
Thomas Golin Almeida
Department of Chemistry, University of Helsinki, Helsinki, 00014, Finland
Institute for Atmospheric and Earth System Research, University of Helsinki, Helsinki, 00014, Finland
Emelda Ahongshangbam
Department of Chemistry, University of Helsinki, Helsinki, 00014, Finland
Institute for Atmospheric and Earth System Research, University of Helsinki, Helsinki, 00014, Finland
Siddharth Iyer
Aerosol Physics Laboratory, Tampere University, Tampere, 33014, Finland
Department of Chemistry, University of Helsinki, Helsinki, 00014, Finland
Institute for Atmospheric and Earth System Research, University of Helsinki, Helsinki, 00014, Finland
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Cited articles
Anglada, J. M., Crehuet, R., and Francisco, J. S.: The stability of α-hydroperoxyalkyl radicals, Chemistr, 22, 18092–18100, 2016. a
Bannwarth, C., Ehlert, S., and Grimme, S.: GFN2-xTB-An accurate and broadly parametrized self-consistent tight-binding quantum chemical method with multipole electrostatics and density-dependent dispersion contributions, J. Chem. Theory Comput., 15, 1652–1671, 2019. a
Berndt, T., Richters, S., Kaethner, R., Voigtländer, J., Stratmann, F., Sipilä, M., Kulmala, M., and Herrmann, H.: Gas-phase ozonolysis of cycloalkenes: formation of highly oxidized RO2 radicals and their reactions with NO, NO2, SO2, and other RO2 radicals, J. Phys. Chem. A, 119, 10336–10348, 2015. a
Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M., Roldin, P., Berndt, T., Crounse, J., Wennberg, P., Mentel, T., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D., Thornton, J., Donahue, N., Kjaergaard, H., and Ehn, M.: Highly oxygenated organic molecules (HOM) from gas-phase autoxidation involving peroxy radicals: A key contributor to atmospheric aerosol, Chem. Rev., 119, 3472–3509, 2019. a
Boyd, C. M., Sanchez, J., Xu, L., Eugene, A. J., Nah, T., Tuet, W. Y., Guzman, M. I., and Ng, N. L.: Secondary organic aerosol formation from the β-pinene+NO3 system: effect of humidity and peroxy radical fate, Atmos. Chem. Phys., 15, 7497–7522, https://doi.org/10.5194/acp-15-7497-2015, 2015. a
Chai, J.-D. and Head-Gordon, M.: Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections, Phys. Chem. Chem. Phys., 10, 6615–6620, 2008. a
Cleary, P. A., Wooldridge, P. J., Millet, D. B., McKay, M., Goldstein, A. H., and Cohen, R. C.: Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations, Atmos. Chem. Phys., 7, 1947–1960, https://doi.org/10.5194/acp-7-1947-2007, 2007. a
Dada, L., Stolzenburg, D., Simon, M., Fischer, L., Heinritzi, M., Wang, M., Xiao, M., Vogel, A., Ahonen, L., Amorim, A., Baalbaki, R., Baccarini, A., Baltensperger, U., Bianchi, F., Dällenbach, K., DeVivo, J., Dias, A., Dommen, J., Duplissy, J., Finkenzeller, H., Hansel, A., He, X.-C., Hofbauer, V., Hoyle, C., Kangasluoma, J., Kim, C., Kürten, A., Kvashnin, A., Mauldin, R., Makhmutov, V., Marten, R., Mentler, B., Nie, W., Petäjä, T., Quéléver, L., Saathoff, H., Tauber, C., Tome, A., Molteni, U., Volkamer, R., Wagner, R., Wagner, A., Wimmer, D., Winkler, P., Yan, C., Zha, Q., Rissanen, M., Gordon, H., Curtius, J., Worsnop, D., Lehtipalo, K., Donahue, N., Kirkby, J., Haddad, I., and Kulmala, M.: Role of sesquiterpenes in biogenic new particle formation, Sci. Adv., 9, eadi5297, https://doi.org/10.1126/sciadv.adi5297, 2023. a
Day, D. A., Fry, J. L., Kang, H. G., Krechmer, J. E., Ayres, B. R., Keehan, N. I., Thompson, S. L., Hu, W., Campuzano-Jost, P., Schroder, J. C., Stark, H., DeVault, M. P., Ziemann, P. J., Zarzana, K. J., Wild, R. J., Dubè, W. P., Brown, S. S., and Jimenez, J. L.: Secondary organic aerosol mass yields from NO3 oxidation of α-pinene and Δ-carene: Effect of RO2 radical fate, J. Phys. Chem. A, 126, 7309–7330, 2022. a
Draper, D. C., Farmer, D. K., Desyaterik, Y., and Fry, J. L.: A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2, Atmos. Chem. Phys., 15, 12267–12281, https://doi.org/10.5194/acp-15-12267-2015, 2015. a
Draper, D., Almeida, T. G., Iyer, S., Smith, J. N., Kurtén, T., and Myllys, N.: Unpacking the diversity of monoterpene oxidation pathways via nitrooxy–alkyl radical ring-opening reactions and nitrooxy–alkoxyl radical bond scissions, J. Aerosol Sci., 179, 106379, https://doi.org/10.1016/j.jaerosci.2024.106379, 2024. a, b, c, d, e, f, g, h, i, j, k, l, m
Draper, D. C., Myllys, N., Hyttinen, N., Møller, K. H., Kjaergaard, H. G., Fry, J. L., Smith, J. N., and Kurtén, T.: Formation of Highly Oxidized Molecules from NO3 Radical Initiated Oxidation of Δ-3-Carene: A Mechanistic Study, ACS Earth and Space Chem., 3, 1460–1470, 2019. a
Dunning Jr., T. H.: Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen, J. Chem. Phys., 90, 1007–1023, 1989. a
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I.-H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén, T., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., Canagaratna, M., Maso, M. D., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V.-M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476–479, 2014. a
Gao, C. W., Allen, J. W., Green, W. H., and West, R. H.: Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms, Comput. Phys. Commun., 203, 212–225, 2016. a
Glasius, M. and Goldstein, A. H.: Recent discoveries and future challenges in atmospheric organic chemistry, Environ. Sci. Technol., 50, 2754–2764, 2016. a
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. a
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. a
Hantschke, L., Novelli, A., Bohn, B., Cho, C., Reimer, D., Rohrer, F., Tillmann, R., Glowania, M., Hofzumahaus, A., Kiendler-Scharr, A., Wahner, A., and Fuchs, H.: Atmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: rate constants and product yields, Atmos. Chem. Phys., 21, 12665–12685, https://doi.org/10.5194/acp-21-12665-2021, 2021. a
Hariharan, P. C. and Pople, J. A.: The influence of polarization functions on molecular orbital hydrogenation energies, Theor. Chim. Acta, 28, 213–222, 1973. a
Hasan, G., Salo, V.-T., Valiev, R. R., Kubecka, J., and Kurten, T.: Comparing reaction routes for 3 (RO
Iyer, S., Reiman, H., Møller, K. H., Rissanen, M. P., Kjaergaard, H. G., and Kurten, T.: Computational investigation of RO2 + HO2 and RO2 + RO2 reactions of monoterpene derived first-generation peroxy radicals leading to radical recycling, J. Phys. Chem. A, 122, 9542–9552, 2018. a
Iyer, S., Rissanen, M. P., Valiev, R., Barua, S., Krechmer, J. E., Thornton, J., Ehn, M., and Kurtén, T.: Molecular mechanism for rapid autoxidation in α-pinene ozonolysis, Nat. Commun., 12, 878, https://doi.org/10.1038/s41467-021-21172-w, 2021. a
Jokinen, T., Sipilä, M., Junninen, H., Ehn, M., Lönn, G., Hakala, J., Petäjä, T., Mauldin III, R. L., Kulmala, M., and Worsnop, D. R.: Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF, Atmos. Chem. Phys., 12, 4117–4125, https://doi.org/10.5194/acp-12-4117-2012, 2012. a
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, https://doi.org/10.5194/acp-5-1053-2005, 2005. a
Karppinen, I., Pasik, D., Ahongshangbam, E., and Myllys, N.: The impact of unimolecular reactions on the possibility of acyl peroxy radical initiated isoprene oxidation, Aerosol Res., 3, 175–183, https://doi.org/10.5194/ar-3-175-2025, 2025. a
Kurtén, T., Møller, K. H., Nguyen, T. B., Schwantes, R. H., Misztal, P. K., Su, L., Wennberg, P. O., Fry, J. L., and Kjaergaard, H. G.: Alkoxy radical bond scissions explain the anomalously low secondary organic aerosol and organonitrate yields from α-pinene + NO3, J. Phys. Chem. Lett., 8, 2826–2834, 2017. a, b, c, d, e
Lee, A., Goldstein, A. H., Kroll, J. H., Ng, N. L., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes, J. Geophys. Res.-Atmos., 111, https://doi.org/10.1029/2005JD006437, 2006. a
Liu, J., D'Ambro, E. L., Lee, B. H., Schobesberger, S., Bell, D. M., Zaveri, R. A., Zelenyuk, A., Thornton, J. A., and Shilling, J. E.: Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors, Environ. Sci. Technol., 56, 12066–12076, 2022. a
Liu, Y., Shen, H., Mu, J., Li, H., Chen, T., Yang, J., Jiang, Y., Zhu, Y., Meng, H., Dong, C., Wang, W., and Xue, L.: Formation of peroxyacetyl nitrate (PAN) and its impact on ozone production in the coastal atmosphere of Qingdao, North China, Sci. Total Environ., 778, 146265, https://doi.org/10.1016/j.scitotenv.2021.146265, 2021. a
Lun, X., Lin, Y., Chai, F., Fan, C., Li, H., and Liu, J.: Reviews of emission of biogenic volatile organic compounds (BVOCs) in Asia, J. Environ. Sci., 95, 266–277, 2020. a
Møller, K. H., Otkjær, R. V., Hyttinen, N., Kurtén, T., and Kjaergaard, H. G.: Cost-effective implementation of multiconformer transition state theory for peroxy radical hydrogen shift reactions, J. Phys. Chem. A, 120, 10072–10087, 2016. a
Myllys, N., Elm, J., Halonen, R., Kurtén, T., and Vehkamäki, H.: Coupled cluster evaluation of the stability of atmospheric acid–base clusters with up to 10 molecules, J. Phys. Chem. A, 120, 621–630, 2016a. a
Myllys, N., Elm, J., and Kurten, T.: Density functional theory basis set convergence of sulfuric acid-containing molecular clusters, Computat. Theor. Chem., 1098, 1–12, 2016b. a
Nozière, B. and Fache, F.: Reactions of organic peroxy radicals, RO2, with substituted and biogenic alkenes at room temperature: unsuspected sinks for some RO2 in the atmosphere?, Chem. Sci., 12, 11676–11683, 2021. a
Nozière, B. and Vereecken, L.: H-shift and cyclization reactions in unsaturated alkylperoxy radicals near room temperature: propagating or terminating autoxidation?, Phys. Chem. Chem. Phys., 26, 25373–25384, 2024. a
Nozière, B., Durif, O., Dubus, E., Kylington, S., Emmer, Å., Fache, F., Piel, F., and Wisthaler, A.: The reaction of organic peroxy radicals with unsaturated compounds controlled by a non-epoxide pathway under atmospheric conditions, Phys. Chem. Chem. Phys., 25, 7772–7782, 2023. a
Orlando, J. J. and Tyndall, G. S.: Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance, Chem. Soc. Rev., 41, 6294–6317, 2012. a
Pasik, D.: Monoterpene oxidation pathways initiated by acyl peroxy radical addition, Zenodo [data set], https://doi.org/10.5281/zenodo.14892593, 2025. a
Pasik, D., Iyer, S., and Myllys, N.: Cost-effective approach for atmospheric accretion reactions: a case of peroxy radical addition to isoprene, Phys. Chem. Chem. Phys., 26, 2560–2567, 2024b. a
Pracht, P., Bohle, F., and Grimme, S.: Automated exploration of the low-energy chemical space with fast quantum chemical methods, Phys. Chem. Chem. Phys., 22, 7169–7192, 2020. a
Presto, A. A., Huff Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from terpene ozonolysis. 1. Effect of UV radiation, Environ. Sci. Technol., 39, 7036–7045, 2005. a
Riplinger, C., Sandhoefer, B., Hansen, A., and Neese, F.: Natural Triple Excitations in Local Coupled Cluster Calculations with Pair Natural Orbitals, J. Chem. Phys., 139, 134101, https://doi.org/10.1063/1.4821834, 2013. a
Riplinger, C., Pinski, P., Becker, U., Valeev, E. F., and Neese, F.: Sparse Maps–A Systematic Infrastructure for Reduced-Scaling Electronic Structure Methods. II. Linear Scaling Domain Based Pair Natural Orbital Coupled Cluster Theory, J. Chem. Phys., 144, 024109, https://doi.org/10.1063/1.4939030, 2016. a
Rissanen, M. P.: NO2 suppression of autoxidation–inhibition of gas-phase highly oxidized dimer product formation, ACS Earth and Space Chemistry, 2, 1211–1219, 2018. a
Rissanen, M., Kurten, T., Sipilä, M., Thornton, J., Kangasluoma, J., Sarnela, N., Junninen, H., Jorgensen, S., Schallhart, S., Kajos, M., Taipale, R., Springer, M., Mentel, T., Ruuskanen, T., Petäjä, T., Worsnop, D., Kjaergaard, H., and Ehn, M.: The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene, J. Am. Chem. Soc., 136, 15596–15606, 2014. a
Seal, P., Barua, S., Iyer, S., Kumar, A., and Rissanen, M.: A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals, Phys. Chem. Chem. Phys., 25, 28205–28212, 2023. a
Shrivastava, M., Cappa, C., Fan, J., Goldstein, A., Guenther, A., Jimenez, J., Kuang, C., Laskin, A., Martin, S., Ng, N., Petäjä, T., Pierce, J., Rasch, P., Roldin, P., Seinfeld, J., Shilling, J., Smith, J., Thornton, J., Volkamer, R., Wang, J., Worsnop, D., Zaveri, R., Zelenyuk, A., and Zhang, Q.: Recent advances in understanding secondary organic aerosol: Implications for global climate forcing, Rev. Geophys., 55, 509–559, 2017. a
Skodje, R. T., Truhlar, D. G., and Garrett, B. C.: A general small-curvature approximation for transition-state-theory transmission coefficients, J. Phys. Chem., 85, 3019–3023, 1981. a
Spracklen, D. V., Jimenez, J. L., Carslaw, K. S., Worsnop, D. R., Evans, M. J., Mann, G. W., Zhang, Q., Canagaratna, M. R., Allan, J., Coe, H., McFiggans, G., Rap, A., and Forster, P.: Aerosol mass spectrometer constraint on the global secondary organic aerosol budget, Atmos. Chem. Phys., 11, 12109–12136, https://doi.org/10.5194/acp-11-12109-2011, 2011. a
Tee, L. S., Gotoh, S., and Stewart, W. E.: Molecular parameters for normal fluids. Lennard-Jones 12-6 Potential, Ind. Eng. Chem. Fund., 5, 356–363, 1966. a
Vereecken, L. and Nozière, B.: H migration in peroxy radicals under atmospheric conditions, Atmos. Chem. Phys., 20, 7429–7458, https://doi.org/10.5194/acp-20-7429-2020, 2020. a
Vereecken, L. and Peeters, J.: The 1, 5-H-shift in 1-butoxy: A case study in the rigorous implementation of transition state theory for a multirotamer system, J. Chem. Phys., 119, 5159–5170, 2003. a
Vereecken, L., Nguyen, T., Hermans, I., and Peeters, J.: Computational study of the stability of α-hydroperoxyl-or α-alkylperoxyl substituted alkyl radicals, Chem. Phys. Lett., 393, 432–436, 2004. a
Vereecken, L., Vu, G., Wahner, A., Kiendler-Scharr, A., and Nguyen, H.: A structure activity relationship for ring closure reactions in unsaturated alkylperoxy radicals, Phys. Chem. Chem. Phys., 23, 16564–16576, 2021. a
Viegas, L.: A Multiconformational Transition State Theory Approach to OH Tropospheric Degradation of Fluorotelomer Aldehydes, Chem. Phys. Chem., 24, https://doi.org/10.1002/cphc.202300259, 2023. a
Xu, L., Guo, H., Boyd, C. M., Klein, M., Bougiatioti, A., Cerully, K. M., Hite, J. R., Isaacman-VanWertz, G., Kreisberg, N. M., Knote, C., Olson, K., Koss, A., Goldstein, A. H., Hering, S. V., de Gouw, J., Baumann, K., Lee, S.-H., Nenes, A., Weber, R. J., and Ng, N. L.: Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States, P. Natl. Acad. Sci. USA, 112, 37–42, 2015. a
Xu, L., Pye, H. O. T., He, J., Chen, Y., Murphy, B. N., and Ng, N. L.: Experimental and model estimates of the contributions from biogenic monoterpenes and sesquiterpenes to secondary organic aerosol in the southeastern United States, Atmos. Chem. Phys., 18, 12613–12637, https://doi.org/10.5194/acp-18-12613-2018, 2018. a
Zhang, F. and Dibble, T. S.: Impact of tunneling on hydrogen-migration of the n-propylperoxy radical, Phys. Chem. Chem. Phys., 13, 17969–17977, 2011. a
Zhang, H., Yee, L. D., Lee, B. H., Curtis, M. P., Worton, D. R., Isaacman-VanWertz, G., Offenberg, J. H., Lewandowski, M., Kleindienst, T. E., Beaver, M. R., Holder, A. L., Lonneman, W. A., Docherty, K. S., Jaoui, M., Pye, H. O. T., Hu, W., Day, D. A., Campuzano-Jost, P., Jimenez, J. L., Guo, H., Weber, R. J., de Gouw, J., Koss, A. R., Edgerton, E. S., Brune, W., Mohr, C., Lopez-Hilfiker, F. D., Lutz, A., Kreisberg, N. M., Spielman, S. R., Hering, S. V., Wilson, K. R., Thornton, J. A., and Goldstein, A. H.: Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States, P. Natl. Acad. Sci. USA, 115, 2038–2043, 2018. a
Zhao, D. F., Kaminski, M., Schlag, P., Fuchs, H., Acir, I.-H., Bohn, B., Häseler, R., Kiendler-Scharr, A., Rohrer, F., Tillmann, R., Wang, M. J., Wegener, R., Wildt, J., Wahner, A., and Mentel, Th. F.: Secondary organic aerosol formation from hydroxyl radical oxidation and ozonolysis of monoterpenes, Atmos. Chem. Phys., 15, 991–1012, https://doi.org/10.5194/acp-15-991-2015, 2015. a
Zhao, Q., Møller, K. H., Chen, J., and Kjaergaard, H. G.: Cost-effective implementation of multiconformer transition state theory for alkoxy radical unimolecular reactions, J. Phys. Chem. A, 126, 6483–6494, 2022. a
Zheng, W., Flocke, F. M., Tyndall, G. S., Swanson, A., Orlando, J. J., Roberts, J. M., Huey, L. G., and Tanner, D. J.: Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere, Atmos. Chem. Phys., 11, 6529–6547, https://doi.org/10.5194/acp-11-6529-2011, 2011. a
Short summary
We used quantum chemistry methods to investigate the oxidation mechanisms of acyl peroxy radicals (APRs) with various monoterpenes. Our findings reveal unique oxidation pathways for different monoterpenes, leading to either chain-terminating products or highly reactive intermediates that can contribute to particle formation in the atmosphere. This research highlights APRs as potentially significant but underexplored atmospheric oxidants that may influence future approaches to modelling climate.
We used quantum chemistry methods to investigate the oxidation mechanisms of acyl peroxy...
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