Excitation transport in solution: A quantitative comparison between GAF theory and time-resolved fluorescence profiles

Journal Article · Sun Mar 01 04:00:00 EST 1987 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.452072· OSTI ID:7149704

Hart, D E; Anfinrud, P A; Struve, W S

Time-correlated single photon counting was used to monitor fluorescence concentration depolarization for DODCI in glycerol. For DODCI concentrations below --10/sup -3/ M, the present experiments have minimized self-absorption and excitation trapping artifacts to the extent where they contribute negligibly to the observed differences between experimental fluorescence profiles and profiles computed from the Gochanour--Andersen--Fayer three-body theory for excitation transport in solution. The three-body theory accurately describes fluorescence depolarization at the lower dye concentrations. At higher concentrations, the measured decay in G/sup s/(t), the probability that the excitation resides on the laser-excited molecule, is perceptibly slower than predicted by the three-body theory. This deviation may arise from nonrandom dye distributions in solution, rather than from errors in the three-body theory. The experimental decay is equally well described at all concentrations by an earlier analytic theory which was developed by Huber, Hamilton, and Barnett.

• Research Organization: Department of Chemistry and Ames Laboratory--USDOE Iowa State University, Ames, Iowa 50011
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 7149704
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 86:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
DISPERSIONS
DYES
EMISSION SPECTRA
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITATION
FLUORESCENCE
FUNCTIONS
GLYCEROL
GREEN FUNCTION
HYDROXY COMPOUNDS
LUMINESCENCE
MIXTURES
ORGANIC COMPOUNDS
QUANTITY RATIO
SOLUTIONS
SPECTRA