A computational study of the ozonolysis of sabinene

被引:14
作者
Almatarneh, M. H. [1 ,2 ]
Elayan, I. A. [1 ]
Altarawneh, M. [3 ,4 ]
Hollett, J. W. [5 ]
机构
[1] Univ Jordan, Dept Chem, Amman 11942, Jordan
[2] Mem Univ, Dept Chem, St John, NF A1B 3X7, Canada
[3] Murdoch Univ, Sch Engn & Informat Technol, Perth, WA, Australia
[4] Al Hussein Bin Talal Univ, Dept Chem Engn, Maan, Jordan
[5] Univ Winnipeg, Dept Chem, Winnipeg, MB, Canada
关键词
Criegee intermediate; Epoxide; Ozonolysis; Primary ozonide; Sabinene; Vinyl hydroperoxide; GAS-PHASE REACTIONS; SECONDARY ORGANIC AEROSOL; OH RADICAL FORMATION; CRIEGEE INTERMEDIATE; RATE CONSTANTS; MONOTERPENES; MECHANISM; SERIES; WATER; O-3;
D O I
10.1007/s00214-019-2420-7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
引用
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页数:14
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