Reactivity of the anti-Criegee intermediate of β-pinene with prevalent atmospheric species

  • Ismael A. ElayanEmail author
  • Mansour H. AlmatarnehEmail author
  • Joshua W. HollettEmail author
Original Research


The reaction of the anti-Criegee intermediate (anti-CI) of β-pinene with prevalent atmospheric species has been investigated using quantum-chemical calculations. The calculations predict that the ozone addition to CI occurs with a Gibbs energy of activation (ΔG) of 77 kJ mol−1. The CI reaction with CH4, C2H6, NH3, and chlorinated ethanes is not energetically favored and has high barriers in the range of 253 to 362 kJ mol−1. The more probable reaction with SO2 forms a secondary ozonide (SOZ) intermediate with a barrier of 9 kJ mol−1, while the ΔG to dissociation is 101 kJ mol−1. Among the reactions studied, the one with \( \dot{\mathrm{N}} \)O had the lowest ΔG for its rate-determining step. The ΔG values of the first step addition of O3, NH3, SO2, and \( \dot{\mathrm{N}} \)O do not exceed 84 kJ mol−1. In contrast to previous predictions, the \( \dot{\mathrm{N}} \)O reaction with the CI did not proceed through cyclic adduct formation. The findings agree with previous studies which found that CIs act as oxidizing agents, converting SO2 to SO3, and \( \dot{\mathrm{N}} \)O to \( \dot{\mathrm{N}} \)O2. Thus, the CIs of biogenic compounds should be added to the list of atmospheric oxidizing agents along with O3, NO3, and OH radicals.


Criegee Secondary Ozonide Ozonolysis Oxidation Bimolecular reactions 



We gratefully acknowledge the University of Manitoba for the compute time.

Funding information

M. H. Almatarneh thanks the Deanship of Academic Research at The University of Jordan for a research grant. J. W. Hollett thanks the Natural Sciences and Engineering Research Council of Canada (NSERC) for a Discovery Grant.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2019_1288_MOESM1_ESM.docx (13.9 mb)
ESM 1 The potential energy surface (PES), full-optimized geometries, IRC analyses, electronic energies, cartesian coordinates, and vibrational frequencies. This material is available free of charge via the Internet. (DOCX 14221 kb)


  1. 1.
    Sindelarova K, Granier C, Bouarar I et al (2014) Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years. Atmos Chem Phys 14:9317–9341Google Scholar
  2. 2.
    Guenther AB, Jiang X, Heald CL et al (2012) 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 5:1471–1492Google Scholar
  3. 3.
    Guenther A, Hewitt C, Erickson D (1995) A global model of natural volatile organic compound emissions. J Geophys Res Atmos 100:8873–8892Google Scholar
  4. 4.
    Calvert J, Orlando J, Stockwell W, Wallington T (2015) The mechanisms of reactions influencing atmospheric ozone. Oxford University Press, New YorkGoogle Scholar
  5. 5.
    Waring MS (2016) Secondary organic aerosol formation by limonene ozonolysis: parameterizing multi-generational chemistry in ozone- and residence time-limited indoor environments. Atmos Environ 144:79–86Google Scholar
  6. 6.
    Niu X, Ho SSH, Ho KF et al (2016) Indoor secondary organic aerosols formation from ozonolysis of monoterpene: an example of d-limonene with ammonia and potential impacts on pulmonary inflammations. Sci Total Environ 579:212–220PubMedGoogle Scholar
  7. 7.
    Nguyen TL, Peeters J, Vereecken L (2009) Theoretical study of the gas-phase ozonolysis of β-pinene (C10H16). Phys Chem Chem Phys 11:5643–5656PubMedGoogle Scholar
  8. 8.
    Grosjean D, Williams EL, Grosjean E et al (1993) Atmospheric oxidation of biogenic hydrocarbons: reaction of ozone with β-pinene, D-limonene and trans-caryophyllene. Environ Sci Technol 27:2754–2758Google Scholar
  9. 9.
    Shu Y, Atkinson R (1994) Rate constants for the gas-phase reactions of O3 with a series of terpenes and OH radical formation from the O3 reactions with sesquiterpenes at 296 ± 2 K. In J Chem Kinet 26:1193–1205Google Scholar
  10. 10.
    Hakola H, Arey J, Aschmann SM, Atkinson R (1994) Product formation from the gas-phase reactions of OH radicals and O3 with a series of monoterpenes. J Atmos Chem 18:75–102Google Scholar
  11. 11.
    Atkinson R, Hasegawa D, Aschmann SM (1990) Rate constants for the gas-phase reactions of O3 with a series of monoterpenes and related compounds at 296 ± 2 K. In J Chem Kinet 22:871–887Google Scholar
  12. 12.
    Criegee R (1975) Mechanism of Ozonolysis. Angew Chem Int Ed Engl 14:745–752Google Scholar
  13. 13.
    Almatarneh MH, Elayan IA, Poirier RA, Altarawneh M (2017) The ozonolysis of cyclic monoterpenes: a computational review. Can J Chem 96:281–292Google Scholar
  14. 14.
    Rinne J, Hakola H, Laurila T, Rannik Ü (2000) Canopy scale monoterpene emissions of Pinus sylvestris dominated forests. Atmos Environ 34:1099–1107Google Scholar
  15. 15.
    Street RA, Owen S, Duckham SC et al (1997) Effect of habitat and age on variations in volatile organic compound (VOC) emissions from Quercus ilex and Pinus pinea. Atmos Environ 31:89–100Google Scholar
  16. 16.
    Hakola H, Rinne J, Laurila T (1998) The hydrocarbon emission rates of tea-leafed willow (Salix phylicifolia), silver birch (Betula pendula) and european aspen (Populus tremula). Atmos Environ 32:1825–1833Google Scholar
  17. 17.
    Pérez-Rial D, Peñuelas J, López-Mahía P, Llusià J (2009) Terpenoid emissions from Quercus robur. A case study of Galicia (NW Spain). J Environ Monit 11:1268–1275PubMedGoogle Scholar
  18. 18.
    Owen S, Boissard C, Street RA et al (1997) Screening of 18 mediterranean plant species for volatile organic compound emissions. Atmos Environ 31:101–117Google Scholar
  19. 19.
    Pankow JF, Seinfeld JH, Asher WE, Erdakos GB (2001) Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the α-pinene/, β-pinene/, sabinene/, Δ3-carene/, and cyclohexene/ozone systems. Environ Sci Technol 35:1164–1172PubMedGoogle Scholar
  20. 20.
    Amin HS, Hatfield ML, Huff Hartz KE (2013) Characterization of secondary organic aerosol generated from ozonolysis of α-pinene mixtures. Atmos Environ 67:323–330Google Scholar
  21. 21.
    Griffin R, Cocker D (1999) Organic aerosol formation from the oxidation of biogenic hydrocarbons. J Geophys Res Atmos 104:3555–3567Google Scholar
  22. 22.
    Hatakeyama S, Izumi K, Fukuyama T, Akimot H (1989) Reactions of ozone with α-pinene and β-pinene in air: yields of gaseous and particulate products. J Geophys Res 94:13Google Scholar
  23. 23.
    Hasson AS, Kuwata T, Paulson SE (2001) Production of stabilized Criegee intermediates and peroxides in the gas phase ozonolysis of alkenes: 2. Asymmetric and biogenic alkenes. J Geophys Res Atmos 106:143–153Google Scholar
  24. 24.
    Ma Y, Marston G (2008) Multifunctional acid formation from the gas-phase ozonolysis of β-pinene. Phys Chem Chem Phys 10:6115–6126PubMedGoogle Scholar
  25. 25.
    Winterhalter R, Neeb P, Grossmann D et al (2000) Products and mechanism of the gas phase reaction of ozone with β-pinene. J Atmos Chem 35:165–197Google Scholar
  26. 26.
    Hatakeyama S, Akimoto H (1994) Reactions of Criegee intermediates in the gas phase. Res Chem Intermed 20:503–524Google Scholar
  27. 27.
    Zhang D, Zhang R (2005) Ozonolysis of α-pinene and β-pinene: kinetics and mechanism. J Chem Phys 122:114308PubMedGoogle Scholar
  28. 28.
    Atkinson R, Aschmann SM, Arey J, Shorees B (1992) Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes. J Geophys Res Atmos 97:6065–6073Google Scholar
  29. 29.
    Vereecken L, Harder H, Novelli A (2014) The reactions of Criegee intermediates with alkenes, ozone, and carbonyl oxides. Phys Chem Chem Phys 16:4039–4049PubMedGoogle Scholar
  30. 30.
    Yu J, Cocker DR, Griffin RJ et al (1999) Gas-phase ozone oxidation of monoterpenes: gaseous and particulate products. J Atmos Chem 34:207–258Google Scholar
  31. 31.
    Curci G, Beekmann M, Vautard R et al (2009) Modelling study of the impact of isoprene and terpene biogenic emissions on European ozone levels. Atmos Environ 43:1444–1455Google Scholar
  32. 32.
    Sartelet KN, Couvidat F, Seigneur C, Roustan Y (2012) Impact of biogenic emissions on air quality over Europe and North America. Atmos Environ 53:131–141Google Scholar
  33. 33.
    Kampa M, Castanas E (2008) Human health effects of air pollution. Environ Pollut 151:362–367PubMedGoogle Scholar
  34. 34.
    Oliveira RCM, Bauerfeldt GF (2015) Ozonolysis reactions of monoterpenes: a variational transition state investigation. J Phys Chem A 119:2802–2812PubMedGoogle Scholar
  35. 35.
    Zhang X, Chen Z, Wang H et al (2009) An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications. Atmos Environ 43:4465–4471Google Scholar
  36. 36.
    Lin XX, Liu YR, Huang T et al (2014) Theoretical studies of the hydration reactions of stabilized Criegee intermediates from the ozonolysis of β-pinene. RSC Adv 4:28490–28498Google Scholar
  37. 37.
    Kumar M, Busch DH, Subramaniam B, Thompson WH (2014) Criegee intermediate reaction with CO: mechanism, barriers, conformer-dependence, and implications for ozonolysis chemistry. J Phys Chem A 118:1887–1894PubMedGoogle Scholar
  38. 38.
    Kurtén T, Bonn B, Vehkamäki H, Kulmala M (2007) Computational study of the reaction between biogenic stabilized Criegee intermediates and sulfuric acid. J Phys Chem A 111:3394–3401PubMedGoogle Scholar
  39. 39.
    Khamaganov VG, Hites RA (2001) Rate constants for the gas-phase reactions of ozone with isoprene, α- and β-pinene, and limonene as a function of temperature. J Phys Chem A 105:815–822Google Scholar
  40. 40.
    Nolting F, Behnke W, Zetzsch C (1988) A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH. J Atmos Chem 6:47–59Google Scholar
  41. 41.
    Johnson D, Rickard AR, McGill CD, Marston G (2000) The influence of orbital asymmetry on the kinetics of the gas-phase reactions of ozone with unsaturated compounds. Phys Chem Chem Phys 2:323–328Google Scholar
  42. 42.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li H, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Jr PJE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision A.02. Gaussian, Inc., WallingfordGoogle Scholar
  43. 43.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648Google Scholar
  44. 44.
    Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789Google Scholar
  45. 45.
    Chai JD, Head-Gordon M (2008) Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Phys Chem Chem Phys 10:6615Google Scholar
  46. 46.
    Zhao Y, Truhlar DG (2008) 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 function. Theor Chem Accounts 120:215–241Google Scholar
  47. 47.
    Fukui K (1981) The path of chemical reactions – the IRC approach. Acc Chem Res 14:363–368Google Scholar
  48. 48.
    Miliordos E, Xantheas SS (2016) The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth. Angew Chem Int Ed 55:1015–1019Google Scholar
  49. 49.
    Su YT, Huang YH, Witek HA, Lee YP (2013) Infrared absorption spectrum of the simplest Criegee intermediate CH2OO. Science 340:174–176PubMedGoogle Scholar
  50. 50.
    Almatarneh MH, Al-Shamaileh E, Ahmad ZM et al (2017) A computational study of the ozonolysis of phenanthrene. Acta Phys Pol A 132:3–11Google Scholar
  51. 51.
    Wei WM, Zheng RH, Pan YL et al (2014) Ozone dissociation to oxygen affected by Criegee intermediate. J Phys Chem A 118:1644–1650PubMedGoogle Scholar
  52. 52.
    Xu K, Wang W, Wei W et al (2017) Insights into the reaction mechanism of Criegee intermediate CH2OO with methane and implications for the formation of methanol. J Phys Chem A 121:7236–7245PubMedGoogle Scholar
  53. 53.
    Jørgensen S, Gross A (2009) Theoretical investigation of the reaction between carbonyl oxides and ammonia. J Phys Chem A 113:10284–10290PubMedGoogle Scholar
  54. 54.
    Khalil MAK (1999) Reactive chlorine compounds in the atmosphere. Springer-Verlag, BerlinGoogle Scholar
  55. 55.
    Makide Y, Rowland FS (1981) Tropospheric concentrations of methylchloroform, CH3CCl3, in January 1978 and estimates of the atmospheric residence times for hydrohalocarbons. Proc Natl Acad Sci U S A 78:5933–5937PubMedPubMedCentralGoogle Scholar
  56. 56.
    Prinn RG, Rasmussen RA, Simmonds PG et al (1983) The atmospheric lifetime experiment 5. Results for CH3CCl3 based on three years of data. J Geophys Res 88:8415–8426Google Scholar
  57. 57.
    Na K, Song C, Switzer C, Cocker DR (2007) Effect of ammonia on secondary organic aerosol formation from α-pinene ozonolysis in dry and humid conditions. Environ Sci Technol 41:6096–6102PubMedGoogle Scholar
  58. 58.
    Huang H-L, Chao W, Lin JJ-M (2015) Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2. Proc Natl Acad Sci 112:10857–10862PubMedGoogle Scholar
  59. 59.
    Ahrens J, Carlsson PTM, Hertl N et al (2014) Infrared detection of Criegee intermediates formed during the ozonolysis of β-pinene and their reactivity towards sulfur dioxide. Angew Chem Int Ed 53:715–719Google Scholar
  60. 60.
    Jiang L, Xu Y, Ding A (2011) Reaction of stabilized Criegee intermediates from ozonolysis of limonene with sulfur dioxide: ab initio and DFT study. J Phys Chem A 114:12452–12461Google Scholar
  61. 61.
    Almatarneh MH, Elayan IA, Altarawneh M, Hollett JW (2018) Hydration and secondary ozonide of the Criegee intermediate of sabinene. ACS Omega 3:2417–2427Google Scholar
  62. 62.
    Vereecken L, Francisco JS (2012) Theoretical studies of atmospheric reaction mechanisms in the troposphere. Chem Soc Rev 41:6217–6708Google Scholar
  63. 63.
    Almatarneh MH, Elayan IA, Abu-Saleh AA-AA et al (2018) The gas-phase ozonolysis reaction of methylbutenol: a mechanistic study. Int J Quantum Chem e25888:1–14. Google Scholar
  64. 64.
    Na K, Song C, Cocker DR (2006) Formation of secondary organic aerosol from the reaction of styrene with ozone in the presence and absence of ammonia and water. Atmos Environ 40:1889–1900Google Scholar
  65. 65.
    Seinfeld JH (1989) Urban air pollution: state of the science. Science 243:745–752PubMedGoogle Scholar
  66. 66.
    Welz O, Savee JD, Osborn DL et al (2012) Direct kinetic measurements of Criegee intermediate (CH2OO) formed by reaction of CH2I with O2. Science 335:204–207PubMedGoogle Scholar
  67. 67.
    Sadezky A, Winterhalter R, Kanawati B et al (2008) Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee intermediate as oligomer chain unit. Atmos Chem Phys 8:2667–2699Google Scholar

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Authors and Affiliations

  1. 1.Department of ChemistryUniversity of ManitobaWinnipegCanada
  2. 2.Department of ChemistryUniversity of JordanAmmanJordan
  3. 3.Chemistry DepartmentMemorial University of NewfoundlandSt. John’sCanada
  4. 4.Department of ChemistryUniversity of WinnipegWinnipegCanada

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