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Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China
China Waterborne Transport Research Institute, Beijing 100088, China
* Author to whom correspondence should be addressed.
Received: 5 January 2013; in revised form: 7 February 2013 / Accepted: 4 March 2013 / Published: 12 March 2013
Abstract: The mechanism of the chemical reaction of H2O with three stabilized Criegee intermediates (stabCI-OO, stabCI-CH3-OO and stabCIx-OO) produced via the limonene ozonolysis reaction has been investigated using ab initio and DFT (Density Functional Theory) methods. It has been shown that the formation of the hydrogen-bonded complexes is followed by two different reaction pathways, leading to the formation of either OH radicals via water-catalyzed H migration or of α-hydroxy hydroperoxide. Both pathways were found to be essential sources of atmospheric OH radical and H2O2 making a significant contribution to the formation of secondary aerosols in the Earth’s atmosphere. The activation energies at the CCSD(T)/6-31G(d) + CF level of theory were found to be in the range of 14.70–21.98 kcal mol−1. The formation of α-hydroxy hydroperoxide for the reaction of stabCIx-OO and H2O with the activation energy of 14.70 kcal mol−1 is identified as the most favorable pathway.
Keywords: volatile organic chemicals (VOCs); ozone; ab initio methods; ozonolysis reaction mechanisms; limonene
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Jiang, L.; Lan, R.; Xu, Y.-S.; Zhang, W.-J.; Yang, W. Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study. Int. J. Mol. Sci. 2013, 14, 5784-5805.
Jiang L, Lan R, Xu Y-S, Zhang W-J, Yang W. Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study. International Journal of Molecular Sciences. 2013; 14(3):5784-5805.
Jiang, Lei; Lan, Ru; Xu, Yi-Sheng; Zhang, Wen-Jie; Yang, Wen. 2013. "Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study." Int. J. Mol. Sci. 14, no. 3: 5784-5805.