The effects of experimental geometry on the theoretical polarizations of the S1 ← S0 and S2 ← S0 bands of π→π* type in riboflavin have been examined. Polarizations of these two bands are characterized by an angle between them in the range of 20—28° and are relatively insensitive to the input geometry. Thus the predicted polarizations are generally in agreement with fluorescence polarization spectrum of riboflavin at 77°K. Alloxazine forms a strong complex with KI, and the fluorescence and phosphorescence from the charge transfer states have been characterized by means of luminescence and photoselection measurements. Riboflavin did not form a strong complex with KI, but it forms aggregates (dimer) more readily than alloxazine. The excited states of flavins can be populated by the weak dipole-dipole coupling mechanism of energy transfer from 1La states of indoles to the S2 state of flavins. The measured critical distances estimated from the fluorescence depolarization experiments range from 31 Å for indole to 40 A for indole-2-carboxylic acid in glycerol-methanol mixture (9:1) at 263°K.
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