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Theoretical study on rate constants for the reactions of CF3CH2NH2 (TFEA) with the hydroxyl radical at 298 K and atmospheric pressure

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Abstract

Theoretical investigations are carried out on reaction mechanism of the reactions of CF3CH2NH2 (TFEA) with the OH radical by means of ab initio and DFT methods. The electronic structure information on the potential energy surface for each reaction is obtained at MPWB1K/6-31+G(d,p) level and energetic information is further refined by calculating the energy of the species with a Gaussian-2 method, G2(MP2). The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. Our calculation indicates that the H abstraction from –NH2 group is the dominant reaction channel because of lower energy barrier. The rate constants of the reaction calculated using canonical transition state theory (CTST) utilizing the ab initio data. The agreement between the theoretical and experimental rate constants is good at the measured temperature. From the comparison with CH3CH2NH2, it is shown that the fluorine substution decreases the reactivity of the C-H bond.

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Acknowledgments

One of the authors, BKM is thankful to University Grants Commission, New Delhi for providing Dr. D. S. K. Post doctoral fellowship.

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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 study on rate constants for the reactions of CF3CH2NH2 (TFEA) with the hydroxyl radical at 298 K and atmospheric pressure. J Mol Model 19, 2189–2195 (2013). https://doi.org/10.1007/s00894-013-1762-7

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