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Theoretical studies on OH and Cl initiated hydrogen atom abstraction of HFE-227pc (CF3OCF2CHF2)

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Abstract

The kinetics of hydrogen atom abstraction reactions of HFE-227pc by OH and Cl was studied by ab initio method. The structural optimization and frequency calculation of the titled compound and the species formed during the abstraction reactions were performed with density functional theory using hybrid meta density functional MPWB1K with 6–31 + G(d,p) basis set. The energy of the species was further refined by making a single point energy calculation at G3B3 level of theory. The standard enthalpies of formation of reactant and the radical formed after H-atom abstraction was calculated using isodesmic method. The rate constants of abstraction reactions were calculated using Conventional Transition State Theory (CTST) and were found to be 1.5 × 10−15 and 0.53 × 10−16 cm3molecule−1 s−1 for OH and Cl respectively. The calculated value for the abstraction by OH is close to the experimental value of 2.26 × 10−15 cm3molecule−1 s−1 whereas the same for Cl is found to be about five times lower than that of 2.70 × 10−16 cm3molecule−1 s−1. The theoretical studies yielded the enthalpies of formation and the rate constants that are vital in determining the lifetime of HFE-227pc.

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Acknowledgements

The financial assistance provided by CSIR, New Delhi, University Grants Commission (SAP) and UP State Government under its Center of Excellence Program for establishing the computational facility is highly acknowledged. One of the authors (PKR) is thankful to UGC, New Delhi for awarding the Rajiv Gandhi National Fellowship.

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  1. Department of Chemistry, DDU Gorakhpur University, Gorakhpur, 273 009, Uttar Pradesh, India

    Hari Ji Singh, Pradeep Kumar Rao & Laxmi Tiwari

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  1. Hari Ji Singh
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  2. Pradeep Kumar Rao
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  3. Laxmi Tiwari
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Correspondence to Hari Ji Singh.

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Singh, H.J., Rao, P.K. & Tiwari, L. Theoretical studies on OH and Cl initiated hydrogen atom abstraction of HFE-227pc (CF3OCF2CHF2). J Atmos Chem 70, 257–268 (2013). https://doi.org/10.1007/s10874-013-9266-5

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  • DOI: https://doi.org/10.1007/s10874-013-9266-5

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