Murdoch University Research Repository

Welcome to the Murdoch University Research Repository

The Murdoch University Research Repository is an open access digital collection of research
created by Murdoch University staff, researchers and postgraduate students.

Learn more

A computational study of the ozonolysis of sabinene

Almatarneh, M.H., Elayan, I.A., Altarawneh, M.ORCID: 0000-0002-2832-3886 and Hollett, J.W. (2019) A computational study of the ozonolysis of sabinene. Theoretical Chemistry Accounts, 138 (2). Article number 30.

Link to Published Version: https://doi.org/10.1007/s00214-019-2420-7
*Subscription may be required

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.

Item Type: Journal Article
Murdoch Affiliation(s): School of Engineering and Information Technology
Publisher: Springer New York LLC
Copyright: © 2019, Springer-Verlag GmbH Germany, part of Springer Nature
URI: http://researchrepository.murdoch.edu.au/id/eprint/43468
Item Control Page Item Control Page