title: Theoretical study and rate constants calculation for the reactions X + CF3CH2OCF3 (X = F, Cl, Br).
abstract: The multiple-channel reactions X + CF3CH2OCF3 (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6-31 + G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200–2000 K. The theoretical three-parameter expressions for the three channels k1a(T) = 1.24 x 10(-15T1.24)exp(-304.81/T), k2a(T) = 7.27 x 10(-15T0.37)exp(-630.69/T), and k3a(T) = 2.84 x 10(-19T2.51)exp(-2725.17/T) cm3 molecule(-1) s(-1) are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered.
authors.affiliation: College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China. hust_zhanghui11@hotmail.com
authors.forename: Hui
authors.initials: H
authors.lastname: Zhang
authors.forename: Yang
authors.initials: Y
authors.lastname: Liu
authors.forename: Jing-Yao
authors.initials: JY
authors.lastname: Liu
authors.forename: Ze-Sheng
authors.initials: ZS
authors.lastname: Li