Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution
文献类型：期刊论文
| 作者 | Wu, Weiqiang; Yang, Chunfan; Zhao, Hongmei; Liu, Kunhui; Su, Hongmei |
| 刊名 | JOURNAL OF CHEMICAL PHYSICS
 |
| 出版日期 | 2010-03-28 |
| 卷号 | 132期号:12 |
| 关键词 | Association Bonds (Chemical) Fourier Transform Spectra Free Radicals Ground States Infrared Spectra Isomerisation Organic Compounds Photochemistry Photodissociation Reaction Kinetics Solvent Effects Time Resolved Spectra Triplet State |
| ISSN号 | 0021-9606 |
| DOI | 10.1063/1.3352421 |
| 英文摘要 | By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of alpha,beta-enones, acrolein (CH2 = CHCHO) in CH3CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH3CH = C = O with a branching ratio of 0.78 and the less important channel is the alpha cleavage of C - H bond yielding radical fragments CH2 = CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet (3)(pi pi(*)) state rather than the ground S-0 state and the alpha cleavage of C - H bond is more likely to proceed in the singlet S-1 (1)(n pi(*)) state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect. |
| 语种 | 英语 |
| WOS记录号 | WOS:000276209700034 |
| 出版者 | AMER INST PHYSICS |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/69379]  |
| 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,Yang, Chunfan,Zhao, Hongmei,et al. Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution[J]. JOURNAL OF CHEMICAL PHYSICS,2010,132(12). |
| APA | Wu, Weiqiang,Yang, Chunfan,Zhao, Hongmei,Liu, Kunhui,&Su, Hongmei.(2010).Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution.JOURNAL OF CHEMICAL PHYSICS,132(12). |
| MLA | Wu, Weiqiang,et al."Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution".JOURNAL OF CHEMICAL PHYSICS 132.12(2010). |
入库方式： OAI收割
来源：化学研究所
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