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| Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with Sihcl3 | |
| 引用本文： | 张庆竹,王少坤,顾月姝. Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with Sihcl3[J]. 中国化学, 2002, 20(3): 214-219. DOI: 10.1002/cjoc.20020200303 |
| 作者姓名： | 张庆竹 王少坤 顾月姝 |
| 作者单位： | ZHANG，Qing-Zhu WANG，Shao-Kun GU，Yue-ShuSchool of Chemistry and Chemical Engineering，Shandong University，Jinan，Shandong 250100，China |
| 基金项目： | ProjectsupportedbytheResearchFundfortheDoctoralProgramoftheMinistryofEducationofChina (No .19990 42 2 0 1) |
| 摘 要： | ＴｒｉｃｈｌｏｒｏｓｉｌａｎｅｉｓａｎｉｍｐｏｒｔａｎｔｍａｔｅｒｉａｌｉｎｐｌａｓｍａＣｈｅｍｉｃａｌＶａｐｏｒＤｅｐｏｓｉｔｉｏｎ (ＣＶＤ)ａｎｄｉｎｓｅｍｉｃｏｎｄｕｃｔｏｒｄｅｖｉｃｅｐｒｏｃｅｓｓ .1 4 Ｔｈｅｒｅａｃｔｉｏｎｏｆｔｒｉｃｈｌｏｒｏｓｉｌａｎｅｗｉｔｈａｔｏｍｉｃｈｙｄｒｏｇｅｎ ,ｔｈｅｓｉｍｐｌｅｓｔｆｒｅｅ ｒａｄｉｃａｌｓｐｅｃｉｅｓ,ｈａｓｄｒａｗｎｃｏｎｓｉｄｅｒａｂｌｅａｔｔｅｎｔｉｏｎ :ｋｉｎｅｔｉｃｐａｒａｍｅｔｅｒｓｆｏｒＨ ａｔｏｍｒｅａｃｔｉｏｎａｒｅｄ… |
| 关 键 词： | 从头计算法 动力学研究 分离反应 氢 三氯化氢硅 |
Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with SiHCl_3 |
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| ZHANG,Qing-Zhu WANG,Shao-Kun GU,Yue-ShuSchool of Chemistry and Chemical Engineering,Shandong University,Jinan,Shandong ,China. Ab initio Calculation and Kinetic Study for the Abstraction Reaction of H with SiHCl_3[J]. Chinese Journal of Chemistry, 2002, 20(3): 214-219. DOI: 10.1002/cjoc.20020200303 | |
| Authors: | ZHANG Qing-Zhu WANG Shao-Kun GU Yue-ShuSchool of Chemistry Chemical Engineering Shandong University Jinan Shandong China |
| Affiliation: | ZHANG,Qing-Zhu WANG,Shao-Kun GU,Yue-ShuSchool of Chemistry and Chemical Engineering,Shandong University,Jinan,Shandong 250100,China |
| Abstract: | 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) T2.30 exp (‐250/T) [in unit of mL/ (molecule · s). The calculated CVT/SCT rate constants match well with the experimental values. |
| Keywords: | Trichlorosilane abstraction reaction variational transition state |
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