Slow photoionization via higher excited states of N,N-dimethylaniline in ethanol solution probed by femtosecond transient absorption spectroscopy under two-pulse two-photon excitation.

Photoionization dynamics of N,N-dimethylaniline (DMA) from highly electronically excited states in ethanol solution was investigated by means of femtosecond two-pulse two-photon excitation transient absorption (2PE-TA) spectroscopy. The first pump pulse prepares the lowest singlet excited state (S state) of DMA, and the second one excites the S state into higher excited states. In the case with the second pulse at 500 nm, the ionization took place via a rapid channel (<100 fs) and a slow one with the time constant of ∼10 ps. The excitation wavelength effect of the second pulse indicated that a specific electronic state produced directly from higher excited states was responsible for the slow ionization. By integrating these results with the time evolution of the transient absorption spectra of the solvated electron in neat ethanol detected by the simultaneous two-photon excitation, it was revealed that the slow ionization of DMA in ethanol was regulated by the formation of the anionic species just before the completion of the solvation of the electron, leading to the solvated electron in the relaxed state. From these results, it was strongly suggested that the capture of the electron of the Rydberg-like state by the solvent or solvent cluster regulates the appearance of the cation radical.