| 2-甲基噻吩光异构化成3-甲基噻吩的理论研究 |
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| 引用本文： | 王艳霞,陈益山,叶松. 2-甲基噻吩光异构化成3-甲基噻吩的理论研究[J]. 高等学校化学学报, 2005, 26(4): 747-750 |
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| 作者姓名： | 王艳霞 陈益山 叶松 |
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| 作者单位： | 1. 云南大学化学材料工程学院化学系, 昆明 650091;2. 曲靖师范学院化学系, 曲靖 655000 |
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| 摘 要： | 用CASSCF方法以6-31G基组研究了2-甲基噻吩光异构化为3-甲基噻吩的光化学反应和基态(S0)及三重激发态(T1)的相关势能面.反应主要发生在三重态(T1)上,其间经历了两个双自由基,1个三元环中间体及4个过渡态.沿着反应路径找到了2个T1/S0势能面交叉点,其结构都类似于双自由基.在第二个T1/S0势能面交叉点附近由T1向S0的系间窜越(ISC)最为有利.
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| 关 键 词： | 2-甲基噻吩 3-甲基噻吩 CASSCF 势能面交叉点 反应路径 光异构化反应 |
| 文章编号： | 0251-0790(2005)04-0747-04 |
| 收稿时间： | 2004-03-01 |
Theoretical Study of the Photoisomerization of 2-Methylthiophene to 3-Methylthiophene |
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| WANG Yan-Xia,CHEN Yi-Shan,YE Song. Theoretical Study of the Photoisomerization of 2-Methylthiophene to 3-Methylthiophene[J]. Chemical Research In Chinese Universities, 2005, 26(4): 747-750 |
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| Authors: | WANG Yan-Xia CHEN Yi-Shan YE Song |
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| Affiliation: | 1. Department of Chemistry, School of Chemistry and Material Engineering, Yinnan University, Kunming 650091, China;2. Department of Chemistry, Qujing Normal University, Qujing 655000, China |
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| Abstract: | The photoisomerization of 2-methylthiophene to 3-methylthiophene was studied at the CASSCF level with a 6-31G* basis set. The reaction channels on the ground state(S_0) and excited state(T_1) were investigated. The reaction proceeds via two diradical intermediates, one intermediate product and four transitions states on the T_1 surface. The two-diradical T_1/S_0 intersystem crossing points were located along the reaction path. It is most likely that the intersystem crossing from T_1 to S_0 occurs near the second crossing point because 3-methylthiophene can be formed very easily. Based on the computation we come to the conclusion that the intersystem crossing from T_1 to S_0 is the rate-determining step in the reaction. |
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| Keywords: | CASSCF |
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