High-pressure study of the effect of viscosity on fluorescence and photoisomerization of trans-stilbene
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The fluorescence quantum yield phi/sub f/ and the initial photoisomerization rates for trans-stilbene in several deoxygenated solvents were obtained as a function of solvent viscosity at room temperature by using pressures to 11 kbar to alter solvent viscosity. It was observed that in solvents of the same viscosity, phi/sub f/ is generally larger in hydrocarbons than in hydroxylic solvents. Fluorescence lifetimes at 1 atm were measured with a picosecond laser and streak camera allowing calculation of the radiative deactivation rate of the excited singlet state in several solvents. At high viscosities in paraffin oil and glycerol phi/sub f/ approaches a limiting value associated with the complete inhibition of molecular twist. Analysis of the data gives the rates of intersystem crossing (isc) and of viscosity-dependent deactivation via twist of the planar excited singlet. These parameters indicate that in nonviscous solvents such as n-hexane at room temperature, only about 2% of the planar excited singlet states undergo isc. The isc yield in glycerol at room temperature is calculated to be 21% implying significant isomerization via the triplet state in viscous solvents. 4 figures, 2 tables.
- Research Organization:
- Univ. of Illinois, Urbana
- OSTI ID:
- 6377258
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:1; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALCOHOLS
ALKANES
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
CYCLOALKANES
DEACTIVATION
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EMISSION SPECTROSCOPY
FLUORESCENCE
FLUORESCENCE SPECTROSCOPY
GLYCEROL
HEXANE
HYDROCARBONS
HYDROXY COMPOUNDS
ISOMERIZATION
KINETICS
LASER RADIATION
LUMINESCENCE
MEDIUM PRESSURE
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
PENTANE
PHOTOCHEMICAL REACTIONS
PHOTOGRAPHY
PHOTOLYSIS
PRESSURE DEPENDENCE
RADIATIONS
REACTION KINETICS
SOLVENTS
SPECTROSCOPY
STILBENE
STREAK PHOTOGRAPHY
TIME DEPENDENCE
VERY HIGH PRESSURE
VISCOSITY
400500* -- Photochemistry
ALCOHOLS
ALKANES
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
CYCLOALKANES
DEACTIVATION
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EMISSION SPECTROSCOPY
FLUORESCENCE
FLUORESCENCE SPECTROSCOPY
GLYCEROL
HEXANE
HYDROCARBONS
HYDROXY COMPOUNDS
ISOMERIZATION
KINETICS
LASER RADIATION
LUMINESCENCE
MEDIUM PRESSURE
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
PENTANE
PHOTOCHEMICAL REACTIONS
PHOTOGRAPHY
PHOTOLYSIS
PRESSURE DEPENDENCE
RADIATIONS
REACTION KINETICS
SOLVENTS
SPECTROSCOPY
STILBENE
STREAK PHOTOGRAPHY
TIME DEPENDENCE
VERY HIGH PRESSURE
VISCOSITY