Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with SiHCl_3  

作　　者：张庆竹 王少坤 顾月姝 

出　　处：《Chinese Journal of Chemistry》2002年第3期214-219,共6页中国化学（英文版）

基　　金：ProjectsupportedbytheResearchFundfortheDoctoralProgramoftheMinistryofEducationofChina (No .19990 42 2 0 1)

摘　　要：The mechanism of the reaction of H with SiHCl_3 has been investigated at highlevel of ab initio molecular orbital theory. Theoretical analysis provides a conclusive evidencethat 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 studiedusing 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―3000K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior, a three-parameterrate-temperature formula is fitted as follows; k( T) = (3.24 x 10^(-19)) T^(2.30) exp( - 250/T) [inunit of mL/(molecule·s). The calculated CVT/SCT rate constants match well with the experimentalvalues.The mechanism of the reaction of H with SiHCl_3 has been investigated at highlevel of ab initio molecular orbital theory. Theoretical analysis provides a conclusive evidencethat 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 studiedusing 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―3000K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior, a three-parameterrate-temperature formula is fitted as follows; k( T) = (3.24 x 10^(-19)) T^(2.30) exp( - 250/T) [inunit of mL/(molecule·s). The calculated CVT/SCT rate constants match well with the experimentalvalues.

关 键 词：TRICHLOROSILANE abstraction reaction variational transition state 

分 类 号：O643.1[理学—物理化学]