Dual level direct dynamics study of gas phase reaction of CF3CH2OCH2CF3 with Cl atoms and atmospheric degradation of CF3CH2OCH2CF3

• Published in: Chemical physics letters Vol. 721; pp. 141 - 148
• Main Authors: Lily, Makroni, Baidya, Bidisha, Chandra, Asit K.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 16.04.2019
• Subjects: Atmospheric degradation; CF3CH2OCH2CF3; Cl Atoms; Kinetics; Variational transition state theory; Atmospheric degradation; CF3CH2OCH2CF3; Variational transition state theory; Kinetics; Cl Atoms
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2019.02.037

[Display omitted] •First theoretical studies on the kinetics and mechanism of CF3CH2OCH2CF3 + Cl reaction.•Ab initio CCSD(T) and variational TST (CVT) are used for kinetic modeling.•Atmospheric degradation of CF3CH2OCH2CF3 was studied.•Calculated rate coefficients are in good agreement with the experimental values.•The estimated atmospheric lifetime of CF3CH2OCH2CF3 is 0.14 year. The kinetics and mechanism of H–abstraction reaction between CF3CH2OCH2CF3 and Cl atoms are studied in the temperature range of 250–1000 K using CCSD(T)//BHandHLY/6-311++G(d, p) method and canonical variational transition state theory (CVT). Two potential pathways are observed for H–abstraction reaction and one of them is the predominant channel over the whole temperature range. IRC calculation reveals an indirect reaction process through the formation of pre- and post-reaction complexes. The calculated rate coefficient kCl = 6.95 × 10−13 cm3 molecule−1 s−1 is in good agreement with the experimental results. Reaction with Cl atoms may constitute a significant sink in the marine boundary layer.