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Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with SiHCl 3
Author(s) -
Zhang QingZhu,
Wang ShaoKun,
Gu YueShu
Publication year - 2002
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20020200303
Subject(s) - chemistry , reaction rate constant , ab initio , hydrogen atom abstraction , arrhenius equation , transition state theory , thermodynamics , atmospheric temperature range , computational chemistry , quantum tunnelling , kinetic energy , kinetics , hydrogen , activation energy , quantum mechanics , organic chemistry , physics
Abstract 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.