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Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution
Wu, Weiqiang; Yang, Chunfan; Zhao, Hongmei; Liu, Kunhui; Su, Hongmei
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
2010-03-28
DOI10.1063/1.3352421
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
关键词[WOS]POTENTIAL-ENERGY-SHEETS ; PAUSON-KHAND REACTION ; 193 NM ; MOLECULAR-BEAM ; TRIPLET-STATES ; ACROLEIN ; SPECTROSCOPY ; PHOTOCHEMISTRY ; REARRANGEMENT ; SPECTRA
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
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被引频次:6[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/141762
专题中国科学院大连化学物理研究所
作者单位Chinese Acad Sci, State Key Lab Mol React Dynam, BNLMS, Inst Chem, Beijing 100190, Peoples R China
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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).
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