Mechanism of OH-initiated atmospheric oxidation of E/Z-CF3CF = CFCF3: a quantum mechanical study

Original Paper
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Abstract

A detailed theoretical investigation was performed on the mechanisms for the reactions of E/Z-CF3CF = CFCF3 with OH radicals by means of density functional theory (DFT). The geometries and frequencies of all the stationary points and the minimum energy path (MEP) are calculated at the M06-2X/aug-cc-pVDZ level. To obtain more reliable energy information, the high-level single-point energies are further refined at the MCG3/3 level. Possible reaction pathways including the addition-elimination and the OH-initiated oxidation pathways are considered. A complete description of the possible degradation mechanisms of E/Z-CF3CF = CFCF3 in the absence and presence of O2/NO has been presented. The calculated results demonstrate that the most accessible products are CF3, CF(OH) = CFCF3, CF(O)CHFCF3, CF3C(O)F, and CHFCF3 via the dissociation reactions starting from the addition intermediates IM1E/IM1Z in the absence of O2/NO. While in the atmosphere, IM1E/IM1Z can further react with O2/NO to form the likely products CF3C(O)F and HO2. The calculated results are consistent with the experimental results.

Figure

Mechanism of OH-initiated atmospheric oxidation of E/Z-CF3CF = CFCF3

Keywords

E/Z-CF3CF = CFCF3 OH radicals Reaction mechanism Theoretical calculations 
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Notes

Acknowledgments

This work is supported by the National Nature Science Foundation of China (20973077, 21373098) and the Program for New Century Excellent Talents in University (NCET).

Supplementary material

894_2014_2179_MOESM1_ESM.doc (15.6 mb)
ESM 1 (DOC 15934 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational ChemistryJilin UniversityChangchunPeople’s Republic of China

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