| Theoretical Study of the Low-Lying Excited States of Butoxy Radicals and Non-Radiative Decay Routes |
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| 作者姓名： | 林玲 祖莉莉 方维海 于建国 刘若庄 |
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| 作者单位： | Department of Chemistry, Beijing Normal University, Beijing 100875, China |
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| 基金项目： | Project supported by the National Natural Science Foundation of China （Nos. 20472011, 20673013）, the Scientific Research Foundation for the Returned 0verseas Chinese Scholars by State Education Ministry and the Major State Basic Research Development Program （No. 2004CB719903）. |
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| 摘 要： | The potential energy surfaces for the butoxy radical dissociation into R·＋O on the six low-lying electronic states have been determined with the combined CASSCF and MR-CI methods. The isomerization reactions between the different conformers of 1- and 2-butoxy radicals at the X and B states have been also investigated with the MP2, B3LYP, and CASSCF methods. The non-radiative decay mechanisms of butoxy radicals at the B state have been characterized with the computed potential energy surfaces and intersections. Supported by recent LIF experimental results, it was predicted that the t-butoxy radical would predissociate via the B/C intersection. As to 1- and 2-butoxy radicals, the relative energies of the transition states for the isomerization reactions between conformers at the B state are much lower than those of the B/C intersections, resulting in the predominance of the isomerization in the decay of the B state for 1- and 2-butoxy radicals.
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| 关 键 词： | 激发态 丁醇醚基 非辐射衰变路线 能线图 |
| 修稿时间： | 2007-01-18 |
Theoretical Study of the Low-Lying Excited States of Butoxy Radicals and Non-Radiative Decay Routes |
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| LIN, Ling ZU, Li-Li FANG, Wei-Hai YU, Jian-Guo LIU, Ruo-Zhuang.Theoretical Study of the Low-Lying Excited States of Butoxy Radicals and Non-Radiative Decay Routes[J].Chinese Journal of Chemistry,2007,25(10):1467-1473. |
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| Authors: | LIN Ling ZU Li-Li FANG Wei-Hai YU Jian-Guo LIU Ruo-Zhuang |
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| Institution: | Department of Chemistry, Beijing Normal University, Beijing 100875, China |
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| Abstract: | The potential energy surfaces for the butoxy radical dissociation into R·+O on the six low‐lying electronic states have been determined with the combined CASSCF and MR‐CI methods. The isomerization reactions between the different conformers of 1‐ and 2‐butoxy radicals at the X? and B? states have been also investigated with the MP2, B3LYP, and CASSCF methods. The non‐radiative decay mechanisms of butoxy radicals at the B? state have been characterized with the computed potential energy surfaces and intersections. Supported by recent LIF experimental results, it was predicted that the t‐butoxy radical would predissociate via the B?/ C? intersection. As to 1‐ and 2‐butoxy radicals, the relative energies of the transition states for the isomerization reactions between conformers at the B? state are much lower than those of the B?/C? intersections, resulting in the predominance of the isomerization in the decay of the B? state for 1‐ and 2‐butoxy radicals. |
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| Keywords: | butoxy radicals excited states non-radiative decay Botential energy profile |
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