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Theoretical investigation on the kinetics and branching ratio of the gas phase reaction of sevoflurane with Cl atom

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Abstract

The present work deals with the theoretical investigation on the Cl initiated H-atom abstraction reaction of sevoflurane, (CF3)2CHOCH2F. A dual-level procedure has been adopted for studying the kinetics of the reaction. Geometrical optimization and frequency calculation were performed at DFT(BHandHLYP)/6-311G(d,p) while single-point energy calculation was made at CCSD(T)/6-311G(d,p) level of theory. The intrinsic reaction coordinate (IRC) calculation has also been performed to confirm the smooth transition from the reactant to product through the respective transition state. The rate constants were calculated using conventional transition state theory (TST). It has been found that 99 % of the reaction proceeded via the H-atom abstraction from the –CH2F end of the sevoflurane. The rate constant of the dominant path is found to be 1.13 × 10−13 cm3 molecule−1 s−1. This is in excellent agreement with the reported experimental rate constant of 1.10 × 10−13 cm3 molecule−1 s−1 obtained by relative rate method using FTIR/Smog chamber and LP/LIF techniques.

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Acknowledgments

Authors are thankful to Council of Scientific and Industrial Research (CSIR), New Delhi for providing financial assistance during the course of the present investigation. PKR is thankful to University Grants Commission, New Delhi for providing Rajiv Gandhi National Fellowship (RGNF). Authors are also thankful to UP State Government for providing a grant under its Center of Excellence program and to UGC under SAP program for establishing the computational lab.

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Authors and Affiliations

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

    Hari Ji Singh, Nand Kishor Gour, Pradeep Kumar Rao & Laxmi Tiwari

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  1. Hari Ji Singh
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  2. Nand Kishor Gour
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  3. Pradeep Kumar Rao
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  4. Laxmi Tiwari
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Correspondence to Hari Ji Singh.

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Singh, H.J., Gour, N.K., Rao, P.K. et al. Theoretical investigation on the kinetics and branching ratio of the gas phase reaction of sevoflurane with Cl atom. J Mol Model 19, 4815–4822 (2013). https://doi.org/10.1007/s00894-013-1977-7

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  • DOI: https://doi.org/10.1007/s00894-013-1977-7

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