title: Theoretical study on the reaction CX3 + SiH(CH3)3 (X = H, F).
abstract: Theoretical investigations are carried out on the multiple-channel reactions, CH(3) + SiH(CH(3))(3) → products and CF(3) + SiH(CH(3))(3) → products. The minimum energy paths (MEP) are calculated at the MP2/6-311 + 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 the canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-1500 K. The theoretical rate constants are in good agreement with the available experimental data and are found to be k(1a)(T) = 1.93 × 10(-24) T(3.15) exp(-1214.59/T) and k(2a)(T) = 1.33 × 10(-25) T(4.13) exp(-397.94/T) (in unit of cm(3) molecule(-1) s(-1)). Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel due to the smaller barrier height among five channels considered.
authors: College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People's Republic of China. hust_zhanghui11@hotmail.com
authors: Hui
authors: H
authors: Zhang
authors: Liu
authors: L
authors: Yang
authors: Jing-Yao
authors: JY
authors: Liu
authors: Ze-Sheng
authors: ZS
authors: Li
mesh_terms: D006838:Hydrocarbons / Q000737:chemistry*; D007700:Kinetics; D008697:Methane; D008956:Models, Chemical; D011789:Quantum Theory; D012821:Silanes / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D006838:Hydrocarbons; D012821:Silanes; D008697:Methane