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Theoretical insight on atmospheric chemistry of HFE-365mcf3: reactions with OH radicals, atmospheric lifetime, and fate of alkoxy radicals (CF3CF2CH(O•)OCH3/CF3CF2CH2OCH2O•)

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Abstract

In the present work, theoretical study on the mechanism and kinetics of the gas-phase reactions of CF3CF2CH2OCH3 (HFE-365mcf3) with the OH radicals have been performed using meta-hybrid modern density functional M06-2X in conjunction with 6-31+G(d,p) basis set. Reaction profiles for OH-initiated hydrogen abstraction are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels. Our calculations reveal that hydrogen abstraction from the –CH2 group is thermodynamically more facile than that from the –CH3 group. This is further ascertained by the calculated C-H bond dissociation energy of CF3CF2CH2OCH3 molecule. The rate constants of the titled reactions are computed over the temperature range of 250–450 K. The calculated rate constant value at 298 K is found to be in reasonable agreement with the experimental results. The atmospheric life time of HFE-365mcf3 is estimated to be 42 days. The atmospheric fate of the alkoxy radicals, CF3CF2CH(O•)OCH3 and CF3CF2CH2OCH2O• are also investigated for the first time using the same level of theory. Out of three plausible decomposition channels, our results clearly point out that reaction with O2 is the dominant atmospheric sink for the decomposition of CF3CF2CH(O•)OCH3 radical in the atmosphere.

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Acknowledgments

DB acknowledges CSIR, New Delhi, for financial assistance in form of Senior Research Fellowship. BKM is thankful to University Grants Commission, New Delhi for providing Dr. D. S. Kothari Fellowship.

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Authors and Affiliations

  1. Department of Chemical Sciences, Tezpur University, Tezpur, Napaam, Assam, 784028, India

    Debajyoti Bhattacharjee & Ramesh Chandra Deka

  2. Department of Chemistry, D. N. Government College, Itanagar, Arunachal Pradesh, 791113, India

    Bhupesh Kumar Mishra

Authors
  1. Debajyoti Bhattacharjee
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  2. Bhupesh Kumar Mishra
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  3. Ramesh Chandra Deka
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Correspondence to Bhupesh Kumar Mishra or Ramesh Chandra Deka.

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Bhattacharjee, D., Mishra, B.K. & Deka, R.C. Theoretical insight on atmospheric chemistry of HFE-365mcf3: reactions with OH radicals, atmospheric lifetime, and fate of alkoxy radicals (CF3CF2CH(O•)OCH3/CF3CF2CH2OCH2O•). J Mol Model 21, 69 (2015). https://doi.org/10.1007/s00894-015-2629-x

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  • DOI: https://doi.org/10.1007/s00894-015-2629-x

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