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Theoretical investigation of the gas-phase reactions of CF2ClC(O)OCH3 with the hydroxyl radical and the chlorine atom at 298 K

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Abstract

A Theoretical study on the mechanism of the reactions of CF2ClC(O)OCH3 with the OH radical and Cl atom is presented. Geometry optimization and frequency calculations have been performed at the MPWB1K/6-31+G(d,p) level of theory and energetic information is further refined by calculating the energy of the species using G2(MP2) theory. Transition states are searched on the potential energy surface involved during the reaction channels and each of the transition states are characterized by presence of only one imaginary frequency. The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. Theoretically calculated rate constants at 298 K and atmospheric pressure using the canonical transition state theory (CTST) are found to be in good agreement with the experimentally measured ones. Using group-balanced isodesmic reactions as working chemical reactions, the standard enthalpies of formation for CF2ClC(O)OCH3, CF2ClC(O)OCH2 and CF3C(O)OCH3 are also reported for the first time.

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Acknowledgments

BKM is thankful to University Grants Commission, New Delhi for providing UGC-Dr. D. S. Kothari Post doctoral Fellowship. Authors are also thankful to the reviewers for their constructive suggestions to improve the quality of the manuscripts.

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Authors and Affiliations

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

    Bhupesh Kumar Mishra, Arup Kumar Chakrabartty & Ramesh Chandra Deka

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  1. Bhupesh Kumar Mishra
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  2. Arup Kumar Chakrabartty
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  3. Ramesh Chandra Deka
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Correspondence to Ramesh Chandra Deka.

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Mishra, B.K., Chakrabartty, A.K. & Deka, R.C. Theoretical investigation of the gas-phase reactions of CF2ClC(O)OCH3 with the hydroxyl radical and the chlorine atom at 298 K. J Mol Model 19, 3263–3270 (2013). https://doi.org/10.1007/s00894-013-1865-1

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