Vibronic excitations of large molecules in solution studied by two-color pump–probe experiments on the 20 fs time scale

Abstract

The ultrafast vibronic response of organic dye molecules in solution is studied in pump–probe experiments with 30 fs excitation pulses resonant to S 0–S n transitions. The molecular dynamics is probed either by pulses at the same spectral position or by 20 fs pulses overlapping with both the S 0–S 1 absorption and emission bands. Three contributions on distinctly different time scales are observed in the temporally and spectrally resolved two‐color measurements. In the regime below 50 fs, a strong coherent coupling of the S 0–S n and the S 0–S 1 transitions occurs that is due to coherent vibrational motions in the electronic ground state. This signal is superimposed on the fast bleaching of the electronic ground state, resulting in a steplike increase of transmission. In the range of the S 0–S 1 emission band, one finds a subsequent picosecond rise of transmission that is due to stimulated emission from vibronic S 1 states. The data demonstrate that the relaxation of S n states directly populated by the pump pulses is much faster than the buildup of stimulated emission. This gives insight into different steps of intramolecular vibronic redistribution and is compared to the S n –S 1 relaxation in other molecules.