Abstract
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.
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Acknowledgements
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.
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Almatarneh, M.H., Elayan, I.A., Altarawneh, M. et al. A computational study of the ozonolysis of sabinene. Theor Chem Acc 138, 30 (2019). https://doi.org/10.1007/s00214-019-2420-7
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DOI: https://doi.org/10.1007/s00214-019-2420-7