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Reaction of chlorine radical with tetrahydrofuran: a theoretical investigation on mechanism and reactivity in gas phase

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Abstract

Reaction of chlorine (Cl) radical with heterocyclic saturated ether, tetrahydrofuran has been studied. The detailed reactivity and mechanism of this reaction is analyzed using hybrid density functional theory (DFT), B3LYP and BB1K methods, and aug-cc-pVTZ basis set. To explore the mechanism of the reaction of tetrahydrofuran with Cl radical, four possible sites of hydrogen atom (H) abstraction pathways in tetrahydrofuran were analyzed. The barrier height and rate constants are calculated for the four H-abstraction channels. The BB1K calculated rate constant for α-axial H-abstraction is comparable with the experimentally determined rate constant. It reflects that α-axial H-abstraction is the main degradation pathway of tetrahydrofuran with Cl radical. DFT-based reactivity descriptors are also calculated and these values describe α-axial H-abstraction as the main reaction channel.

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Acknowledgments

S.B. is thankful to Indian Institute of Technology Patna for financial support. The authors are grateful to IIT Patna for providing general research facilities.

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Authors and Affiliations

  1. Department of Chemistry, Indian Institute of Technology, Patna, India, 800013

    Samiyara Begum & Ranga Subramanian

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  1. Samiyara Begum
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  2. Ranga Subramanian
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Correspondence to Ranga Subramanian.

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Supporting information

Cartesian coordinates (Table S1) and calculated unscaled vibrational frequencies (Table S2) for optimized geometries of reactants, transition states, molecular complexes and products at B3LYP/aug-cc-pVTZ level of theory. (DOC 281 kb)

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Begum, S., Subramanian, R. Reaction of chlorine radical with tetrahydrofuran: a theoretical investigation on mechanism and reactivity in gas phase. J Mol Model 20, 2262 (2014). https://doi.org/10.1007/s00894-014-2262-0

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