Femtosecond real-time probing of reactions. 13. Multiphoton dynamics of IHgI

Real-time studies of the dynamics were performed on the reaction of HgI_2 in a molecular beam. Excitation was by either one or multi pump photons (311 nm), leading to two separate sets of dynamics, each of which could be investigated by a time-delayed probe laser (622 nm) that ionized the parent molecule and the fragments by REMPI processes. These dynamics were distinguished by combining the information from transients taken at each mass (HgI_2, HgI, I_2, Hg, and I) with the results of pump (and probe) power dependence studies on each mass. A method of plotting the slope of the intensity dependence against the pump-probe time delay proved essential. In the preceding publication, we detailed the dynamics of the reaction initiated by a one photon excitation to the A-continuum. Here, we present studies of higher-energy states. Multiphoton excitation accesses predissociative states of HgI_2, for which there are crossings into the symmetric and asymmetric stretch coordinates. The dynamics of these channels, which lead to atomic (I or Hg) and diatomic (HgI) fragments, are discussed and related to the nature of the intermediates along the reaction pathway.

Time-resolved studies of neutral and ionized Na_n clusters with femtosecond light pulses

The real-time dynamics of Na_n (n=3-21) cluster multiphoton ionization and fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Three dimensional wave packet motions in the trimer Na_3 ground state X and excited state B have been observed. We report the first study of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na_n^*) with femtosecond laser pulses. The observation of four absorption resonances for the cluster Na_8 with different energy widths and different decay patterns is more difficult to interpret by surface plasmon like resonances than by molecular structure and dynamics. Timeresolved fragmentation of cluster ions Na_n^+ indicates that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.