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The mechanism of the reaction of H with SiHCl 3 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.
The mechanism of the reaction of H with SiHCl 3 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.