Mode-specific vibrational excitation and energy redistribution after ultrafast intramolecular electron transfer

Vibrational relaxation in the electronic ground state initiated by intramolecular back-electron transfer (b-ET) of betaine-30 (B-30) is studied by picosecond time-resolved anti-Stokes Raman spectroscopy. Measurements were carried out with B-30 dissolved in slowly as well as in rapidly relaxing solvents. We observed a risetime of the Raman band with the highest frequency near 1600 cm−1 which is close to the b-ET time τb-ET of B-30. For B-30 dissolved in propylene carbonate (τb-ET∼1 ps), the population of this mode exhibits a rise time of 1 ps whereas vibrational populations between 400 and 1400 cm−1 increase substantially slower. In contrast, in glycerol triacetin (τb-ET∼3.5 ps) and in ethanol (τb-ET∼6 ps) rise times of all modes are close to the respective b-ET times. Within the first few picoseconds, direct vibrational excitation through b-ET is favored for modes with the highest frequencies and high Franck–Condon factors. Later on, indirect channels of population due to vibrational energy redistribution...

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