Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution

doi:10.1063/1.3352421

CORC > 化学研究所 > 中国科学院化学研究所

	Photodissociation and photoisomerization dynamics of CH2 = CHCHO in solution
	Wu, Weiqiang; Yang, Chunfan; Zhao, Hongmei; Liu, Kunhui; Su, Hongmei
刊名	JOURNAL OF CHEMICAL PHYSICS
	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
出版者	AMER INST PHYSICS
WOS记录号	WOS:000276209700034
内容类型	期刊论文
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).