Mapping of wave packets in direct fragmentation via pump–probe frequency integrated fluorescence spectroscopy

We consider femtosecond excitation of a molecule to a dissociative electronic state. The quantum dynamics is recorded via delayed excitation to a higher electronic state and measurement of the total fluorescence from this state detected as a function of delay time. It is shown that the signal can be used to determine the probability density distribution of the outgoing wave packet describing the fragmentation. This, in particular, applies to the case of fragment detection since then the time-dependent signal directly measures the probability flux at a fixed value of the dissociation coordinate. Numerical examples illustrate the procedure.