A computational study of the ozonolysis of sabinene

  • M. H. AlmatarnehEmail author
  • I. A. Elayan
  • M. Altarawneh
  • J. W. Hollett
Regular Article


The ozonolysis of sabinene has been computationally studied at multiple levels of theory. The reaction proceeds through the so-called Criegee mechanism via the formation of a primary ozonide with two different conformations that dissociate into non-interconvertible zwitterionic Criegee intermediate (syn and anti) conformers and a carbonyl compound. The results show that the decomposition of the Criegee intermediate proceeds through different dissociation pathways. Possible pathways involve the formation of a vinyl hydroperoxide or a dioxirane ester. An alternative novel pathway that does not involve Criegee intermediate formation, but rather epoxide formation, is also investigated. The dissociation of the anti-Criegee intermediate to sabina ketone and OH radicals via the vinyl hydroperoxide pathway is more favorable than the analogous syn-Criegee intermediate dissociation. The calculations show that, between the two competing channels (the ester and vinyl hydroperoxide pathways), the ester pathway is more probable, particularly from the syn-Criegee intermediate. Furthermore, the reactions have been studied in the presence of H2O as a spectator molecule. Interestingly, it had a negligible effect on the energy barrier of the syn-ozone addition as it stabilized all the stationary points. All reactions were found to be strongly exothermic, except in the case of the dissociation of the syn-Criegee intermediate through the vinyl hydroperoxide pathway, where the reaction is endothermic.


Criegee intermediate Epoxide Ozonolysis Primary ozonide Sabinene Vinyl hydroperoxide 



Almatarneh is grateful to the Deanship of Academic Research at the University of Jordan for the grant (Grant Number: 37/2014-2015). The authors also gratefully acknowledge the Atlantic Computational Excellence Network (ACENET) and Compute Canada for the computer time.

Supplementary material

214_2019_2420_MOESM1_ESM.pdf (1.5 mb)
Supplementary material 1 (PDF 1523 kb)


  1. 1.
    Breitmaier E (2006) Terpenes: importance, general structure, and biosynthesis. Wiley, WeinheimCrossRefGoogle Scholar
  2. 2.
    Guenther A, Hewitt C, Erickson D (1995) A global model of natural volatile organic compound emissions. J Geophys Res Atmos 100:8873–8892CrossRefGoogle Scholar
  3. 3.
    Hoffmann T, Odum JR, Bowman F et al (1997) Formation of organic aerosols from the oxidation of biogenic hydrocarbons. J Atmos Chem 26:189–222CrossRefGoogle Scholar
  4. 4.
    Yu J, Cocker DR, Griffin RJ et al (1999) Gas-phase ozone oxidation of monoterpenes: gaseous and particulate products. J Atmos Chem 34:207–258CrossRefGoogle Scholar
  5. 5.
    Oliveira RCDM, Bauerfeldt GF (2012) Thermochemical analysis and kinetics aspects for a chemical model for camphene ozonolysis. J Chem Phys 137:134306CrossRefGoogle Scholar
  6. 6.
    Baptista L, Pfeifer R, Da Silva EC, Arbilla G (2011) Kinetics and thermodynamics of limonene ozonolysis. J Phys Chem A 115:10911–10919CrossRefGoogle Scholar
  7. 7.
    Kesselmeier J, Staudt M (1999) Biogenic volatile organic compounds (VOC): an overview on emission, physiology and ecology. J Atmos Chem 33:23–88CrossRefGoogle Scholar
  8. 8.
    Tollsten L, Müller PM (1996) Volatile organic compounds emitted from beech leaves. Phytochemistry 43:759–762CrossRefGoogle Scholar
  9. 9.
    Owen S, Boissard C, Street RA et al (1997) Screening of 18 Mediterranean plant species for volatile organic compound emissions. Atmos Environ 31:101–117CrossRefGoogle Scholar
  10. 10.
    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 32:1825–1833CrossRefGoogle Scholar
  11. 11.
    Chiappini L, Carrasco N, Temine B et al (2006) Gaseous and particulate products from the atmospheric ozonolysis of a biogenic hydrocarbon, sabinene. Environ Chem 3:286–296CrossRefGoogle Scholar
  12. 12.
    Zhao Y, Zhang R, Wang H et al (2010) Mechanism of atmospheric ozonolysis of sabinene: a DFT study. J Mol Struct THEOCHEM 942:32–37CrossRefGoogle Scholar
  13. 13.
    Griffin R, Cocker D (1999) Organic aerosol formation from the oxidation of biogenic hydrocarbons. J Geophys Res Atmos 104:3555–3567CrossRefGoogle Scholar
  14. 14.
    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 35:1164–1172CrossRefGoogle Scholar
  15. 15.
    Bernard F, Fedioun I, Peyroux F et al (2012) Thresholds of secondary organic aerosol formation by ozonolysis of monoterpenes measured in a laminar flow aerosol reactor. J Aerosol Sci 43:14–30CrossRefGoogle Scholar
  16. 16.
    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 97:6065CrossRefGoogle Scholar
  17. 17.
    Chew AA, Atkinson R (1996) OH radical formation yields from the gas-phase reactions of O3 with alkenes and monoterpenes. J Geophys Res Atmos 101:28649–28653CrossRefGoogle Scholar
  18. 18.
    Aschmann SM, Arey J, Atkinson R (2002) OH radical formation from the gas-phase reactions of O3 with a series of terpenes. Atmos Environ 36:4347–4355CrossRefGoogle Scholar
  19. 19.
    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 18:75–102CrossRefGoogle Scholar
  20. 20.
    Atkinson R, Aschmann SM, Arey J (1990) Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296 ± 2 K. Atmos Environ 24A:2647–2654CrossRefGoogle Scholar
  21. 21.
    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. Int J Chem Kinet 22:871–887CrossRefGoogle Scholar
  22. 22.
    Criegee R (1975) Mechanism of ozonolysis. Angew Chemie Int Ed English 14:745–752CrossRefGoogle Scholar
  23. 23.
    Almatarneh MH, Al-Shamaileh E, Ahmad ZM et al (2017) A computational study of the ozonolysis of phenanthrene. Acta Phys Pol A 132:3–11CrossRefGoogle Scholar
  24. 24.
    Vereecken L, Harder H, Novelli A (2012) The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere. Phys Chem Chem Phys 14:14682CrossRefGoogle Scholar
  25. 25.
    Kjaergaard HG, Kurtén T, Nielsen LB et al (2013) Criegee intermediates react with ozone. J Phys Chem Lett 4:2525–2529CrossRefGoogle Scholar
  26. 26.
    Vereecken L, Harder H, Novelli A (2014) The reactions of Criegee intermediates with alkenes, ozone, and carbonyl oxides. Phys Chem Chem Phys 16:4039–4049CrossRefGoogle Scholar
  27. 27.
    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 118:1887–1894CrossRefGoogle Scholar
  28. 28.
    Jørgensen S, Gross A (2009) Theoretical investigation of the reaction between carbonyl oxides and ammonia. J Phys Chem A 113:10284–10290CrossRefGoogle Scholar
  29. 29.
    Ryzhkov AB, Ariya PA (2006) The importance of water clusters (H2O)n (n = 2,…, 4) in the reaction of Criegee intermediate with water in the atmosphere. Chem Phys Lett 419:479–485CrossRefGoogle Scholar
  30. 30.
    Ryzhkov AB, Ariya PA (2004) A theoretical study of the reactions of parent and substituted Criegee intermediates with water and the water dimer. Phys Chem Chem Phys 6:5042CrossRefGoogle Scholar
  31. 31.
    Ryzhkov AB, Ariya PA (2003) A theoretical study of the reactions of carbonyl oxide with water in atmosphere: the role of water dimer. Chem Phys Lett 367:423–429CrossRefGoogle Scholar
  32. 32.
    Jiang L, Lan R, Xu YS et al (2013) Reaction of stabilized criegee intermediates from ozonolysis of limonene with water: ab initio and DFT study. Int J Mol Sci 14:5784–5805CrossRefGoogle Scholar
  33. 33.
    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 4:28490–28498CrossRefGoogle Scholar
  34. 34.
    Almatarneh MH, Elayan IA, Altarawneh M, Hollett JW (2018) Hydration and secondary ozonide of the Criegee intermediate of sabinene. ACS Omega 3:2417–2427CrossRefGoogle Scholar
  35. 35.
    Almatarneh MH, Elayan IA, Poirier RA, Altarawneh M (2017) The ozonolysis of cyclic monoterpenes: a computational review. Can J Chem 96:281–292CrossRefGoogle Scholar
  36. 36.
    Wang L, Wang L (2017) Mechanism of gas-phase ozonolysis of sabinene in the atmosphere. Phys Chem Chem Phys 19:24209–24218CrossRefGoogle Scholar
  37. 37.
    Frisch MJ, Trucks GW, Schlegel HB, et al (2009) Gaussian 09, Revision A.02. Gaussian, Inc, WallingfordGoogle Scholar
  38. 38.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648CrossRefGoogle Scholar
  39. 39.
    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 37:785–789CrossRefGoogle Scholar
  40. 40.
    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 Acc 120:215–241CrossRefGoogle Scholar
  41. 41.
    Purvis GD, Bartlett RJ (1982) A full coupled-cluster singles and doubles model: the inclusion of disconnected triples. J Chem Phys 76:1910–1918CrossRefGoogle Scholar
  42. 42.
    Pople JA, Head-Gordon M, Raghavachari K (1987) Quadratic configuration interaction. A general technique for determining electron correlation energies. J Chem Phys 87:5968–5975CrossRefGoogle Scholar
  43. 43.
    Zhang D, Zhang R (2005) Ozonolysis of α-pinene and β-pinene: kinetics and mechanism. J Chem Phys 122:114308CrossRefGoogle Scholar
  44. 44.
    Jiang L, Wang W, Xu Y (2010) Ab initio investigation of O3 addition to double bonds of limonene. Chem Phys 368:108–112CrossRefGoogle Scholar
  45. 45.
    Fukui K (1981) The path of chemical reactions—the IRC approach. Acc Chem Res 14:363–368CrossRefGoogle Scholar
  46. 46.
    Nguyen TL, Peeters J, Vereecken L (2009) Theoretical study of the gas-phase ozonolysis of β-pinene (C10H16). Phys Chem Chem Phys 11:5643–5656CrossRefGoogle Scholar
  47. 47.
    Oliveira RCDM, Bauerfeldt GF (2015) Ozonolysis reactions of monoterpenes: a variational transition state investigation. J Phys Chem A 119:2802–2812CrossRefGoogle Scholar
  48. 48.
    Sun T, Wang Y, Zhang C et al (2011) The chemical mechanism of the limonene ozonolysis reaction in the SOA formation: a quantum chemistry and direct dynamic study. Atmos Environ 45:1725–1731CrossRefGoogle Scholar
  49. 49.
    Chuong B, Zhang J, Donahue NM (2004) Cycloalkene ozonolysis: collisionally mediated mechanistic branching. J Am Chem Soc 126:12363–12373CrossRefGoogle Scholar
  50. 50.
    Almatarneh MH, Elayan IA, Abu‐Saleh AAA, Altarawneh M, Ariya PA (2018) The gas-phase ozonolysis reaction of methylbutenol: A mechanistic study. Int J Quantum Chem.

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of JordanAmmanJordan
  2. 2.Chemistry DepartmentMemorial UniversitySt. John’sCanada
  3. 3.School of Engineering and Information TechnologyMurdoch UniversityPerthAustralia
  4. 4.Department of Chemical EngineeringAl-Hussein Bin Talal UniversityMa’anJordan
  5. 5.Department of ChemistryUniversity of WinnipegWinnipegCanada

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