Reaction Mechanisms of a Photo-Induced [1,3] Sigmatropic Rearrangement via a Nonadiabatic Pathway
文献类型：期刊论文
| 作者 | Wu, Weiqiang; Liu, Kunhui; Yang, Chunfan; Zhao, Hongmei; Wang, Huan; Yu, Youqing; Su, Hongmei |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2009-12-17 |
| 卷号 | 113期号:50页码:13892-13900 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp906583u |
| 英文摘要 | Time-resolved Fourier transform infrared absorption spectroscopy measurements and B3LYP/cc-pVDZ calculations have been conducted to characterize the reaction dynamics of a remarkable photoinduced 1,3-Cl sigmatropic rearrangement reaction upon 193 or 266 nm excitation of the model systems acryloyl chloride (CH(2)CHCOCl) and crotonyl chloride (CH(3)CHCHCOCl) ill Solution The reaction is elucidated to follow nonadiabatic pathways via two rapid ISC processes, S(1) -> T(1) and T(1) -> S(0), and the S(1)/T(1) and T(1)/S(0) surface intersections are found to play significant roles leading to the nonadiabatic pathways The S(1) -> T(1) -> S(0) reaction pathway involving the key participation of the T(1) state is the most favorable, corresponding to the lowest energy path. It is also suggested that the photoinduced 1,3-Cl migration reaction of RCHCHCOCl (R = H, CH(3)) proceeds through a stepwise mechanism involving radical dissociation-recombination, which is quite different from the generally assumed one-step concerted process for pericyclic reactions. |
| 语种 | 英语 |
| WOS记录号 | WOS:000272559800008 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/68143]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Su, Hongmei |
| 作者单位 | Chinese Acad Sci, State Key Lab Mol React Dynam, BNLMS, Inst Chem, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wu, Weiqiang,Liu, Kunhui,Yang, Chunfan,et al. Reaction Mechanisms of a Photo-Induced [1,3] Sigmatropic Rearrangement via a Nonadiabatic Pathway[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2009,113(50):13892-13900. |
| APA | Wu, Weiqiang.,Liu, Kunhui.,Yang, Chunfan.,Zhao, Hongmei.,Wang, Huan.,...&Su, Hongmei.(2009).Reaction Mechanisms of a Photo-Induced [1,3] Sigmatropic Rearrangement via a Nonadiabatic Pathway.JOURNAL OF PHYSICAL CHEMISTRY A,113(50),13892-13900. |
| MLA | Wu, Weiqiang,et al."Reaction Mechanisms of a Photo-Induced [1,3] Sigmatropic Rearrangement via a Nonadiabatic Pathway".JOURNAL OF PHYSICAL CHEMISTRY A 113.50(2009):13892-13900. |
入库方式： OAI收割
来源：化学研究所
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