Decay kinetics of the excited S{sub 1} state of the cyanine dye Cy{sup +}I{sup -} (thiacarbocyanine iodide): The computation of quantum yields for different pathways
This work explains the unordinary solvent effect which was observed in the photochemical decay kinetics for the cyanine dye thiacarbocyanine iodide (Cy{sup +}I{sup -}) in binary solvent mixtures toluene/dimethylsulfoxide. The interpretation is formulated in terms of the probability density F(R) describing the distribution of interionic distances R in the ion pair Cy{sup +}I{sup -} and depending on the solvent composition. The proper normalization of this distribution is expressed via the degree of association {alpha} for the ion pair in a given solvent mixture. The {alpha} values are, in turn, extracted by means of the mass action law from the ionic association constants computed in a separate publication. The detailed kinetic scheme includes the empirical parametrization of the R-dependent kinetic constants for different decay channels. The multiparameter fitting procedure represents, with the reasonable parameter values, the dependence of the observed quantum yields on the solvent composition.