Two-dimensional vibronic spectroscopy of molecular predissociation

We calculate two-dimensional (2D) spectra reflecting the time-dependent electronic predissociation of a diatomic molecule. The laser-excited electronic state is coupled non-adiabatically to a fragment channel, leading to the decay of the prepared quasi-bound states. This decay can be monitored by the three-pulse configuration employed in optical 2D spectroscopy. It is shown that in this way it is possible to state-selectively characterize the time-dependent population of resonance states with different lifetimes. A model of the NaI molecule serves as a numerical example. (paper)