We measure the photoionization cross-section of vibrationally excited levels in the S2 state of azulene by femtosecond pump-probe spectroscopy. At the wavelengths studied (349-265 nm in the pump) the transient signals exhibit two distinct and well-defined behaviours : (i) Short-term (on the order of a picosecond) polarization dependent transients and (ii) longer (10 ps – 1 ns) time-scale decays. This letter focuses on the short time transient. In contrast to an earlier study by Diau et al.we unambiguously assign the fast initial decay signal to rotational dephasing of the initial alignment created by the pump transition.
Voir en ligne : Chem. Phys. Lett., 460, 59-63 (2008)