title: Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2and CF3OCF2CF2H &fate of CF3OC(X•)(CF3)2and CF3OCF2CF2X• radicals (X=O, O2).
abstract: In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF3OC(•)(CF3)2and CF3OCF2CF2• in the presence of O2and NO. The subsequent decomposition pathways of CF3OC(O•)(CF3)2and CF3OCF2CF2O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230-350 K are: kT(1)= 5.00 × 10-24T3.57exp(-849.73/T), kT(2)= 1.79 × 10-24T4.84exp(-4262.65/T), kT(3)= 1.94 × 10-24T4.18exp(-884.26/T), and kT(4)= 9.44 × 10-28T5.25exp(-913.45/T) cm3molecule-1s-1.
authors.affiliation: Institute of Functional Material Chemistry, National &Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Feng-Yang
authors.initials: FY
authors.lastname: Bai
authors.affiliation: Institute of Functional Material Chemistry, National &Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Yuan
authors.initials: Y
authors.lastname: Ma
authors.affiliation: Institute of Functional Material Chemistry, National &Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Shuang
authors.initials: S
authors.lastname: Lv
authors.affiliation: Institute of Functional Material Chemistry, National &Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Xiu-Mei
authors.initials: XM
authors.lastname: Pan
authors.affiliation: School of Life Science, Northeast Normal University, 130024 Changchun, People's Republic of China.
authors.forename: Xiu-Juan
authors.initials: XJ
authors.lastname: Jia