Perfluoro-n-alkanes and perfluorocycloalkanes are found to affect the photophysical properties of saturated hydrocarbons in markedly different ways.The addition of a low concentration (<0.2 M) of a perfluoro-n-alkane to a hydrocarbon liquid has no observable effect on the electronic absorption spectrum and only very slightly quenches the hydrocarbon fluorescence. In contrast, at the same concentration levels, the perfluorocycloalkane strongly perturbs the absorption spectrum and very effectively reduces the fluorescence quantum yield. The change in the absorption spectrum is attributed to a contact charge-transfer absorption with the hydrocarbon acting as electron donor. The efficiency with which the perfluorocycloalkane reduces the hydrocarbon fluorescence quantum yield increases with increasing perfluorocycloalkane concentration. The results are analyzed with a conventional diffusional model that includes transient terms. The model contains two parameters, an encounter distance, R, and the product of the relative diffusion coefficient, D, and the lifetime, tau/sub 0/, of the hydrocarbon excited state. The model is applied to perfluorodecalin quenching of cyclohexane, decalin, and 2,3-dimethylbutane at excitation wavelengths, lambda/sub ex/, ranging from 185 to 147 nm. An unrestricted, two-parameter, least-squares fit of the model to the data provides values of R and D(tau/sub 0/) for each solvent system at each lambda/sub ex/. Where values ofmore » D and tau/sub 0/ are known independently, their product agrees well with the D(tau/sub 0/) obtained from the fit. The value of R is found to be approx. = 14 angstrom for all solvents at all lambda/sub ex/. This value is estimated to be about 2 times larger than the ground-state hydrocarbon-perfluorodecalin contact distance.« less