Time-resolved fluorescence is a powerful spectroscopy for investigating the relaxation of the solvent around a polar excited molecule. As shown above, the emission spectrum shifts to lower energy as solvation takes place. To ensure that no ultrafast stage of solvation is missed by the measurements, knowledge of the emission spectrum at time zero, i.e. before relaxations start, is crucial. The latter can be estimated by using the absorption and emission spectra in a nonpolar environment as intrinsic line-shape functions and by adding a broadening function and a shift. The left panel shows that the time-zero emission spectrum obtained experimentally using broadband fluorescence up-conversion spectroscopy (website), as demonstrated by Ernsting and coworkers, coincides with the estimated spectrum. This reveals that the entire relaxation dynamics of the solvent, here ethanol, is captured by our measurements.
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