ABSTRACT
Control over the electronic state of the Ag(3) cluster is approached via a progression of ultrafast photoinduced transitions within the full electronic manifold of the negative to the neutral and finally the cationic state of the system. High-bandwidth supercontinuum laser pulses ranging from 500 to 950 nm are employed for addressing the wide range of electronic resonance conditions associated with the ladder climbing process of a tandem photoelectron detachment and a resonance enhanced multiphoton ionization (REMPI). With the control of the phase over the full spectral envelope of the supercontinuum in a pulse shaper arrangement, pulse forms are generated with the aim of synchronizing ultrashort subpulse sequences to the characteristic dynamics of the system during charge reversal. Pulse forms ranging over several hundred femtoseconds in total duration and subpulse structures down to 15 fs duration with a variable spectral composition can be obtained for this purpose. A free optimization based on a closed-loop genetic algorithm is employed for ordering the subpulse sequences to match the structural evolution of the system. The effective control attainable in this scenario is evaluated in view of maintaining a defined sequence of electronic transitions within the complex dynamic response of the system during the photoexcitation. Further emphasis is made on analyzing the degree of control attainable in the nonlinear regime of multiphoton excitation at supercontinuum bandwidths.
