Coherent nuclear wavepacket motions in ultrafast excited-state intramolecular proton transfer: sub-30-fs resolved pump-probe absorption spectroscopy of 10-hydroxybenzo[h]quinoline in solution.

The dynamics of the excited-state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline (10-HBQ) and the associated coherent nuclear motion were investigated in solution by femtosecond absorption spectroscopy. Sub-picosecond transient absorption measurements revealed spectral features of the stimulated emission and absorption of the keto excited state (the product of the reaction). The stimulated emission band appeared in the 600-800-nm region, corresponding to the wavelength region of the steady-state keto fluorescence. It showed successive temporal changes with time constants of 350 fs and 8.3 ps and then disappeared with the lifetime of the keto excited state (260 ps). The spectral feature of the stimulated emission changed in the 350-fs dynamics, which was likely assignable to the intramolecular vibrational energy redistribution in the keto excited state. The 8.3-ps change caused a spectral blue shift and was attributed to the vibrational cooling process. The excited-state absorption was observed in the 400-600-nm region, and it also showed temporal changes characterized by the 350-fs and 8.3-ps components. To examine the coherent nuclear dynamics (nuclear wavepacket motion) in excited-state 10-HBQ, we carried out pump-probe measurements of the stimulated emission and absorption signals with time resolution as good as 27 fs. The obtained data showed substantially modulated signals due to the excited-state vibrational coherence up to a delay time of several picoseconds after photoexcitation. This means that the vibrational coherence created by photoexcitation in the enol excited state is transferred to the product. Fourier transform analysis indicated that four frequency components in the 200-700-cm(-1) region contribute to the oscillatory signal, corresponding to the coherent nuclear motions in excited-state 10-HBQ. Especially, the lowest-frequency mode at 242 cm(-1) is dephased significantly faster than the other three modes. This observation was regarded as a manifestation that the nuclear motion of the 242-cm(-1) mode is correlated with the structural change of the molecule associated with the reaction (the reaction coordinate). The 242-cm(-1) mode observed in excited-state 10-HBQ was assigned to a vibration corresponding to the ground-state vibration at 243 cm(-1) by referring to the results of resonance Raman measurements and density functional calculations. It was found that the nuclear motion of this lowest-frequency mode involves a large displacement of the OH group toward the nitrogen site as well as in-plane skeletal deformation that assists the oxygen and nitrogen atoms to come closer to each other. We discuss the importance of the nuclear wavepacket motion on a multidimensional potential-energy surface including the vibrational coordinate of the low-frequency modes.