Picosecond IR-UV pump-probe spectroscopic study on the intramolecular vibrational energy redistribution of NH2 and CH stretching vibrations of jet-cooled aniline

Intramolecular vibrational energy redistribution (IVR) of the NH2 symmetric and asymmetric stretching vibrations of jet-cooled aniline has been investigated by picosecond time-resolved IR-UV pump-probe spectroscopy. A picosecond IR laser pulse excited the NH2 symmetric or asymmetric stretching vibration of aniline in the electronic ground state and the subsequent time evolutions of the excited level as well as redistributed levels were observed by a picosecond UV pulse. The IVR lifetimes for symmetric and asymmetric stretches were obtained to be 18 and 34 ps, respectively. In addition, we obtained the direct evidence that IVR proceeds via two-step bath states; that is, the NH2 stretch energy first flows into the doorway state and the energy is further dissipated into dense bath states. The rate constants of the second step were estimated to be comparable to or slower than those of the first step IVR. The relaxation behavior was compared with that of IVR of the OH stretching vibration of phenol Y. Yamada, T. Ebata, M. Kayano, and M. Mikami J. Chem. Phys. 120, 7400 (2004)]. We found that the second step IVR process of aniline is much slower than that of phenol, suggesting a large difference of the "doorway state increasing the dense bath states" anharmonic coupling strength between the two molecules. We also observed IVR of the CH stretching vibrations, which showed much faster IVR behavior than that of the NH2 stretches. The fast relaxation is described by the interference effect, which is caused by the coherent excitation of the quasistationary states.