Pulse shaping effect on two-photon excitation efficiency of alpha-perylene crystals and perylene in chloroform solution

We demonstrated that the two-photon excitation efficiency of perylene in chloroform solution as well as that of crystalline perylene was dramatically increased by optimizing the shape of intense femtosecond laser pulses of a regenerative amplifier output. The efficiency was three times higher than for an unshaped single femtosecond pulse with the pulse width of shorter than 50 fs. The pulse shape optimized for the solution sample was a pulse train with a repetition frequency of about 340 cm(-1), and the pulse shape optimized for crystalline perylene was very similar. These results supported our previous findings on alpha-perylene crystals using weak femtosecond pulses from a mode-locked laser oscillator T. Okada et al. J. Chem. Phys. 121, 6385 (2004)]. Furthermore, it was confirmed that the shaped pulse optimized for the liquid sample could also increase the two-photon excitation efficiency of alpha-perylene crystals and vice versa. We concluded that the mechanism for the increase in excitation efficiency of perylene in chloroform was almost the same as that for alpha-perylene crystal, and that the efficiency increased mainly through intramolecular dynamical processes. Processes involving intermolecular interactions and/or energy states delocalized over the crystal cannot play the major role.