Isomerization Dynamics of Dicyanine A in n-Alcoholic Solution

The radiationless relaxation of dicyanine A molecules in n-alcohols methanol to butanol has been studied by picosecond fluorescence spectroscopy and time-resolved nonlinear spectroscopy. The fluorescence decay rates have been measured as a function of viscosity, temperature, and fluorescence wavelength. It is shown that the wavelength dependence can be explained by coexistence of two ground-state conformers. The intrinsic activation barrier for the nonradiative decay from the excited surface is very small, much less than 1 kcal/mol. In a particular solvent the time constants of the nonradiative relaxation show a linear dependence on the variation of viscosity. The experimental data are discussed in relation to the BFO theory (Bagchi, B.; Fleming, G.R.; Oxtoby, D.W. J. Chem. Phys. 1983, 78: 7375).