Time-resolved fluorescence spectra of three amino-substituted coumarin dyes have been recorded in methanol and dimethyl sulfoxide using the fluorescence upconversion technique with an apparatus response function of ≈200 fs fwhm. The three fluorinated coumarins are the 7-amino-4-trifluoromethylcoumarin (C151), the 7-diethylamino-4-trifluoromethylcoumarin (C35), and the rigidified aminocoumarin with a julolidine structure (C153). The dynamic Stokes shifts are found to be dominated by an ultrafast component with a characteristic time shorter than the present time resolution of ≈50 fs. The dynamic Stokes shifts are compared to estimations based on a “Kamlet and Taft” analysis of steady-state data in 20 solvents. It is found that the ultrafast component can be assigned mainly to intramolecular relaxation. The influences of photoinduced changes of solute−solvent hydrogen bonds on the observed spectral shifts are discussed. The breaking of hydrogen bonds at the amino group is very fast in both solvents and embedded in the ultrafast solvent inertial relaxation, while the reformation of hydrogen bonds at the carbonyl group is believed to occur on the 10−20 ps time scale in the hydrogen bond donating (HBD) solvent methanol. However, it is impossible to unambiguously correlate a particular experimental time constant with the breaking or the formation of a hydrogen bond.

We present experimental results for the cross phase modulation (xpm) induced transient absorption signal in a 1 mm thick fused silica plate using a white light continuum as a probe. The fused silica plate mimics the entrance window of a commercial flow cell commonly used in liquid-phase transient absorption measurements. The experimental results are compared with those obtained theoretically by numerically solving the set of nonlinear coupled wave equations describing the propagation of the pump and the probe. The simulations allow for the different group velocities of the pump and probe pulses, and include the influence of the first and second order dispersion on the continuum probe. From the calculations the physical origin of the complex oscillatory feature observed around the zero time delay of each wavelength of the (chirped) continuum has been accurately identified. The influence of propagation effects arising from the finite thickness of the sample is discussed in great detail, and the necessity to work with thin samples, preferably free-flowing jets, is emphasized. The good agreement between theory and experiment indicates that the xpm artifact may be useful for characterizing the continuum probe, in particular its chirp.