Int. J. Mol. Sci. 2013, 14(3), 5784-5805; doi:10.3390/ijms14035784
Article

Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study

Lei Jiang 1,2 email, Ru Lan 3 email, Yi-Sheng Xu 1,* email, Wen-Jie Zhang 1 email and Wen Yang 1 email
1 State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China 2 College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China 3 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
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
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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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MDPI and ACS Style

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.

AMA Style

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.

Chicago/Turabian Style

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.

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