Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with Sihcl3

The mechanism of the reaction of H with SiHCl₃ has been investigated at high level of ab initio molecular orbital theory. Theoretical analysis provides a conclusive evidence that the main process occurring in this reaction is the hydrogen abstraction from the Si‐H bond, the abstraction of Cl has higher barrier and is difficult to react. The kinetics has been studied using canonical variational transition‐state theory (CVT) with small curvature tunneling effect (SCT) correction. The rate constants have been calculated over a wide temperature range of 200‐3000 K. The CVT/SCT rate constants exhibit typical non‐Arrhenius behavior, a three‐parameter rate‐temperature formula is fitted as follows: k (T) = (3.24 × 10^?19) T^2.30 exp (‐250/T) [in unit of mL/ (molecule · s). The calculated CVT/SCT rate constants match well with the experimental values.