title: Theoretical study and rate constant calculations for the reactions of SiHX₃ with CF₃ and CH₃ radicals (X = F, Cl).
abstract: Theoretical investigations were carried out on the multi-channel reactions CF3 + SiHF3, CF3 + SiHCl3, CH3 + SiHF3, and CH3 + SiHCl3. Electronic structures were calculated at the MP2/6-311+G(d,p) level, and energetic information further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels were calculated by the canonical variational transition state theory with small-curvature tunneling correction over the temperature range of 200-1,500 K. The theoretical rate constants were in good agreement with the available experimental data and were fitted to the three parameter expression: k 1a(T) = 2.93 × 10(-26) T (4.25) exp (-318.68/T), and k 2a(T) = 3.67 × 10(-22) T (2.72) exp (-1,414.22/T), k 3a (T) = 7.00 × 10(-24) T (3.27) exp (-384.04/T), k 4a(T) = 6.35 × 10(-22) T (2.59) exp (-603.18/T) (in unit of cm(3)molecule(-1)s(-1)) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among four 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: Ping
authors.initials: P
authors.lastname: Liu
authors.forename: Jing-Yao
authors.initials: JY
authors.lastname: Liu
authors.forename: Ze-Sheng
authors.initials: ZS
authors.lastname: Li