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题名: Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution
作者: Wu, Weiqiang1;  Yang, Chunfan1;  Zhao, Hongmei1;  Liu, Kunhui1;  Su, Hongmei1
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
刊名: JOURNAL OF CHEMICAL PHYSICS
发表日期: 2010-03-28
DOI: 10.1063/1.3352421
卷: 132, 期:12
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Physics
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.
关键词[WOS]: POTENTIAL-ENERGY-SHEETS ;  PAUSON-KHAND REACTION ;  193 NM ;  MOLECULAR-BEAM ;  TRIPLET-STATES ;  ACROLEIN ;  SPECTROSCOPY ;  PHOTOCHEMISTRY ;  REARRANGEMENT ;  SPECTRA
语种: 英语
WOS记录号: WOS:000276209700034
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/141762
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, State Key Lab Mol React Dynam, BNLMS, Inst Chem, Beijing 100190, Peoples R China

Recommended Citation:
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).
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