| S_2ClF的构型及其异构化反应的密度泛函理论研究 |
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| 引用本文： | 陈文凯,章永凡,徐艺军,李奕,李俊.S_2ClF的构型及其异构化反应的密度泛函理论研究[J].结构化学,2004,23(2):197-201. |
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| 作者姓名： | 陈文凯 章永凡 徐艺军 李奕 李俊 |
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| 作者单位： | 福州大学化学系,结构化学国家重点实验室,福州,350002 |
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| 基金项目： | 国家自然科学基金(20273013)，福建省青年科技人才创新基金(2001J018)，福建省自然科学基金重大项目(2002F010)，福建省教育厅科技项目(JA03020)，福州大学科技发展基金资助项目 |
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| 摘 要： | 采用量子化学中的密度泛函理论B3LYP方法,在6-311+G(3df)水平上,全优化得到了S2ClF线型和分叉型2种异构体的平衡结构,同时对可能发生的分子内卤素原子迁移反应的过渡态进行了考察。计算结果表明,从能量角度看,线型的ClSSF为稳定构型,热力学和动力学计算表明,无论是F原子迁移还是Cl原子迁移,分子内的原子迁移需要较高的活化能,并且速度很慢。
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| 关 键 词： | S2ClF 异构体 密度泛函理论 量子化学 过渡态理论 |
A Density Functional Theory Study on the Structures and Isomerization of ClSSF |
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| CHEN Wen-Kai,ZHANG Yong-Fan,XU Yi-Jun,LI Yi,LI Jun-Qian.A Density Functional Theory Study on the Structures and Isomerization of ClSSF[J].Chinese Journal of Structural Chemistry,2004,23(2):197-201. |
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| Authors: | CHEN Wen-Kai ZHANG Yong-Fan XU Yi-Jun LI Yi LI Jun-Qian |
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| Abstract: | The B3LYP calculations of density functional theory with 6-311 G(3df) basis set level have been used to investigate the equilibrium structures and intramolecular rearrangement reactions of the linear ClSSF and branched SSClF isomers. The calculated results show that the linear structure is more stable than the branched one (by 31.3 kJmol-1 corrected with ZPVE) energetically and the agreement with available experimental values is satisfactory. The predicted energy barriers for the intramolecular F and C1 atom transfer isomeriza- tion processes are 126.4 and 175.8 kJmol-1, respectively. The isomerization process is unlikely to proceed via unimolecular channel because of the much higher energy barriers. |
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| Keywords: | S_2C1F isomerization density functional theory quantum chemistry transition-state theory |
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