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

International Journal of Molecular Sciences

Lei Jiang²  Ru Lan¹  Yi-Sheng Xu²  Wen-Jie Zhang² 

[1] China Waterborne Transport Research Institute, Beijing 100088, China; E-Mail:;State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China; E-Mails:

关键词: volatile organic chemicals (VOCs);    ozone;    ab initio methods;    ozonolysis reaction mechanisms;    limonene;   

DOI  :  10.3390/ijms14035784

来源: mdpi

【 摘 要 】

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.

【 授权许可】

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