Electronic Resource
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
109 (1998), S. 1397-1408
ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The all-trans→13-cis⋅9-cis photoisomerization reaction of retinal in aerated nonpolar solvents has been studied by femtosecond time-resolved ultraviolet-visible (UV-VIS) absorption spectroscopy. The excited-state absorption spectra in the wavelength region 400–800 nm indicate that there is no all-trans→13-cis⋅9-cis isomerization reaction pathway that is complete in the electronic excited singlet manifold of S1, S2, and S3. The ground-state bleaching recovery of all-trans retinal monitored in the near UV (ultraviolet) wavelength region 310–390 nm shows that a perpendicular excited singlet state (p*) takes part in the all-trans→13-cis⋅9-cis isomerization reaction. The lifetime of p* is about 7 ps, and the precursor of p* is most probably the S2 state. The isomerization quantum yield derived from the femtosecond UV absorption data agrees well with those determined by the HPLC analysis of the photoproduct. The temperature dependence of the isomerization quantum yield indicates the existence of a potential-energy barrier as high as (1.2±0.6)×103 cm−1 on the reaction pathway from the S2 state to the p* state. © 1998 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.476692
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