Abstract
The effect of pressure-induced changes in the viscosity of methylcyclohexane (MCH) on the dynamics of the quenching by oxygen of the excited singlet state of 9,10-dimethylanthracene (DMEA) has been investigated using time-resolved fluorescence decay measurements. The decay of fluorescence from aerated and deaerated MCH solutions of DMEA is exponential for applied pressures ranging from 0.1 to 700 MPa. However, the fluorescence decay curves measured for oxygen-saturated MCH solutions of DMEA are distinctly nonexponential over this pressure range. These nonexponential fluorescence decay curves can be described by using a variation of the model developed by Smoluchowski for diffusion-controlled processes in solution in which the rate constant for the quenching reaction, k act, is finite. Analysis of the fluorescence decay data according to this model results in values for the reaction distance, R, and k act of 0.81 nm and 2.6 × 10 10 M −1 s −1, respectively.
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