In:
The Journal of Chemical Physics, AIP Publishing, Vol. 132, No. 12 ( 2010-03-28)
Abstract:
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 α,β-enones, acrolein (CH2CHCHO) 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 CH3CHCO with a branching ratio of 0.78 and the less important channel is the α cleavage of CH bond yielding radical fragments CH2CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet (ππ∗)3 state rather than the ground S0 state and the α cleavage of CH bond is more likely to proceed in the singlet S1 (nπ∗)1 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.
Type of Medium:
Online Resource
ISSN:
0021-9606
,
1089-7690
Language:
English
Publisher:
AIP Publishing
Publication Date:
2010
detail.hit.zdb_id:
3113-6
detail.hit.zdb_id:
1473050-9
