Ionization dynamics of a phenylenediamine derivative in solutions as revealed by femtosecond simultaneous and stepwise two-photon excitation.

Femtosecond transient absorption spectroscopy with off-resonant simultaneous and resonant stepwise two-photon excitation methods were applied to the direct observation of photoionization dynamics of a phenylenediamine derivative in n-hexane, ethanol and acetonitrile solutions. Upon the selective excitation of the solute via the off-resonant two-photon excitation to the energy level almost equivalent with the ionization potential in the gas phase, rapid appearance of the radical cation (within ca. 100-200 fs) was observed in polar and nonpolar solutions. On the other hand, in the case where the excited energy level from the ground state is 0.8 eV lower than the ionization potential in the gas phase, the radical cation appears only in polar solutions in sub-ps to ps time scales, indicating that the photoionization does not occur directly from the highly electronically excited state even in the polar solution. Comparison of the dynamics between ethanol and acetonitrile solutions strongly suggested that the solvation process of the precursor species leading to the ionization took a crucial role in the electron ejection process with lower energy in polar solutions.