title: Time-dependent photoionization of azulene: competition between ionization and relaxation in highly excited states.
abstract: Pump-probe photoionization has been used to map the relaxation processes taking place from highly vibrationally excited levels of the S(2) state of azulene, populated directly or via internal conversion from the S(4) state. Photoelectron spectra obtained by 1+2(') two-color time-resolved photoelectron imaging are invariant (apart from in intensity) to the pump-probe time delay and to the pump wavelength. This reveals a photoionization process which is driven by an unstable electronic state (e.g., doubly excited state) lying below the ionization potential. This state is postulated to be populated by a probe transition from S(2) and to rapidly relax via an Auger-like process onto highly vibrationally excited Rydberg states. This accounts for the time invariance of the photoelectron spectrum. The intensity of the photoelectron spectrum is proportional to the population in S(2). An exponential energy gap law is used to describe the internal conversion rate from S(2) to S(0). The vibronic coupling strength is found to be larger than 60+/-5 microeV.
authors.affiliation: Laboratoire Collisions Agrégats Réactivité, UMR 5589, CNRS, Institut de Recherches sur les Systèmes Atomiques et Moléculaires Complexes, UPS Toulouse, 31062 Toulouse Cedex 04, France. val@irsamc.ups-tlse.fr
authors.forename: Valérie
authors.initials: V
authors.lastname: Blanchet
authors.forename: Kevin
authors.initials: K
authors.lastname: Raffael
authors.forename: Giorgio
authors.initials: G
authors.lastname: Turri
authors.forename: Béatrice
authors.initials: B
authors.lastname: Chatel
authors.forename: Bertrand
authors.initials: B
authors.lastname: Girard
authors.forename: Ivan Anton
authors.initials: IA
authors.lastname: Garcia
authors.forename: Iain
authors.initials: I
authors.lastname: Wilkinson
authors.forename: Benjamin J
authors.initials: BJ
authors.lastname: Whitaker