Journal of Physical Chemistry, Vol.99, No.50, 17700-17710, 1995
Photofragment Imaging of Kr-2 and Arkr Van-der-Waals Molecules Following 2-Photon Excitation
Photofragment imaging is used to study the fragmentation and ionization dynamics of Kr-2 and ArKr upon absorption of two or more photons (lambda = 211-220 nm). For Kr-2 two-photon-excited electronic states are studied that are in energy near Kr (5p) states. All studied Kr-2 two-photon-excited electronic states show competition between ionization and predissociation. The photofragment images also reveal higher order absorption processes in which three-photon absorption of the dimer is followed by dissociation into ground state and excited state Kr fragments. Dissociation after three-photon absorption leads to Kr photofragments, whose recoil can be described by a cos(2) theta distribution with respect to the polarization vector of the laser. For ArKr two, two-photon-excited, electronic bands are observed near Kr (5p) and Ar (4s) transitions. The two-photon-excited ArKr molecules dissociate exclusively into excited state Ar (4s) atoms concomitant with ground state Kr atoms. Therefore, both electronic bands are assigned to Ar*Kr states, i.e. excited states that correlate to Ar (4s) and Kr S-1(0) atomic asymptotes. The Ar photofragment ion images and the multiphoton ionization spectra show competition between ionization and predissociation of these two-photon-excited ArKr states. As with the Kr-2 dimer, the ion images also reveal higher order absorption processes in which three-photon absorption of ArKr is followed by dissociation into neutral Kr ground and Ar excited state fragments. The angular distributions of the fragments formed after predissociation at the two-photon resonant levels and after three-photon absorption are both anisotropic. The recoil of the Ar photofragments after three-photon absorption can be described by a cos(2) theta distribution with respect to the polarization vector of the laser. Markedly different contributions of three-photon absorption and predissociation processes are observed in the ion images of the two electronic bands of ArKr, i.e. three-photon absorption processes are more important than predissociation processes for the electronic band starting at 93 699 cm(-1), whereas predissociation processes are more important than three-photon absorption for the electronic band starting at 94 180 cm(-1).
Keywords:ENHANCED MULTIPHOTON IONIZATION;ULTRAVIOLET-LASER SPECTROSCOPY;RARE-GAS MOLECULES;RADIATIVE LIFETIMES;POTENTIAL CURVES;EXCITED-STATES;RYDBERG STATES;2-PHOTON DISSOCIATION;ELECTRONIC STATES;SPECTRA