The picosecond time-resolved Stokes shift of the laser dye, coumarin 480 (I) is studied in neutral (Triton X-100, TX), cationic (cetyltrimethylammonium bromide, CTAB), and anionic (sodium dodecyl sulfate, SDS) micelles. Above critical micellar concentration (cmc) for all three micelles I exhibits wavelength dependent fluorescence decays and a distinct growth at the long wavelengths. The time dependent Stokes shift studies indicate that the water molecules in the Stern layer of the micelles relax on the time scale 180−550 ps, which is slower than the subpicosecond relaxation dynamics observed in ordinary bulk water.

The picosecond time-resolved Stokes shift of the laser dye coumarin 480 (I) is studied in Aerosol OT-heptane reverse micelles at various concentrations of water. On addition of water to a n-heptane solution of I containing 0.09 M AOT, the emission spectrum of I exhibits a prominent shoulder at 480 nm which is ascribed to the dye molecules in the water pool of the reverse micelles. In n-heptane, the fluorescence decays of I at short and long wavelengths are identical, which rules out any time-resolved Stokes shift. On addition of water to the AOT/heptane system, the decay at long wavelengths exhibit a distinct growth on the nanosecond time scale. This and the time-dependent Stokes shift indicate that the water molecules in the water pool of the AOT reverse micelles undergo slow relaxation on the nanosecond time scale.

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The relative retardation of intramolecular charge transfer (ICT) and the solvation dynamics of coumarin 152 in pure AOT, water, methanol, acetonitrile, and formamide reverse micelles have been investigated using picosecond time-resolved emission spectroscopy. The rate of ICT has been retarded almost 7 times at w 0 = 4 and 4 times at w 0 = 32 compared to that in pure water. The rate of retardation of ICT is also observed in the methanol and acetonitrile reverse micelles in comparison to that in pure methanol and acetonitrile. In pure AOT, the solvation time is 12.22 ns, but at w 0 = 4 of water reverse micelles the solvation time is 7.27 ns. The slow dynamics in methanol, acetonitrile, and formamide reverse micelles is also observed. The relative retardation of the ICT rate is much smaller compared to the several thousand fold decrease in the solvation dynamics in the pool of the reverse micelles. The w dependency of solvation time is observed for water and methanol reverse micelles, but it is little for acetonitrile and none for formamide reverse micelles. The various w dependencies of solvation dynamics in water, methanol, and acetonitrile reverse micelles are explained on the basis of the presence and the absence of hydrogen-bonding networks in water, methanol, and acetonitrile, respectively.

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Abstract. The excited state dynamics of 5-fluorouracil in acetonitrile has been investigated by femtosecond fluorescence upconversion spectroscopy in combination with quantum chemistry TD-DFT calculations ((PCM/TD-PBE0). Experimentally it was found that when going from water to acetonitrile solution the fluorescence decay of 5FU becomes much faster. The calculations show that this is related to the opening of an additional decay channel in acetonitrile solution since the dark n/π* excited state becomes near degenerate with the bright π/π* state, forming a conical intersection close to the FranckCondon region. In both solvents a S 1 -S 0 conical intersection, governed by the out-of-plane motion of the fluorine atom is active, allowing an ultrafast internal conversion to the ground state.