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Theoretical investigation on the atmospheric fate of CF3C(O)OCH2O radical: alpha-ester rearrangement vs oxidation at 298 K

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Abstract

A theoretical study on the mechanism of the thermal decomposition of CF3C(O)OCH2O radical is presented for the first time. Geometry optimization and frequency calculations were performed at the MPWB1K/6–31 + G(d, p) level of theory and energetic information further refined by calculating the energy of the species using G2(MP2) theory. Three plausible decomposition pathways including α-ester rearrangement, reaction with O2 and thermal decomposition (C–O bond scission) were considered in detail. Our results reveal that reaction with O2 is the dominant path for the decomposition of CF3C(O)OCH2O radical in the atmosphere, involving the lowest energy barrier, which is in accord with experimental findings. Our theoretical results also suggest that α-ester rearrangement leading to the formation of trifluoroacetic acid TFA makes a negligible contribution to decomposition of the title alkoxy radical. The thermal rate constants for the above decomposition pathways were evaluated using canonical transition state theory (CTST) at 298 K.

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Acknowledgments

B.K.M. acknowledges financial support from University Grants Commission, New Delhi in form of a UGC-Dr. D.S. Kothari Fellowship.

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Authors and Affiliations

  1. Department of Chemical Sciences, Tezpur University Tezpur, Tezpur, Assam, 784 028, India

    Bhupesh Kumar Mishra

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  1. Bhupesh Kumar Mishra
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Correspondence to Bhupesh Kumar Mishra.

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Mishra, B.K. Theoretical investigation on the atmospheric fate of CF3C(O)OCH2O radical: alpha-ester rearrangement vs oxidation at 298 K. J Mol Model 20, 2444 (2014). https://doi.org/10.1007/s00894-014-2444-9

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