Shaped ultrafast laser pulses were used to study and control the ionization dynamics of electronically excited pyrazine in a pump and probe experiment. For pump pulses created without feedback from the product signal, the ion growth curve (the parent ion signal as a function of pump/probe delay) was described quantitatively by the classical rate equations for internal conversion of the S 2 and S 1 states. Very different, non-classical behavior was observed when a genetic algorithm (GA) was used to minimize the ion signal at some pre-determined target time, T. Two qualitatively different control mechanisms were identified for early (T< 1.5 ps) and late (T> 1.5 ps) target times. In the former case, the ion signal was largely suppressed for t < T , while for t T the ion signal produced by the GA-optimized pulse and a transform limited (TL) pulse coalesced. In contrast, for T > 1.5 ps the ion growth curve followed the classical rate equations for t < T , while for t T the quantum yield for the GA-optimized pulse was much smaller than for a TL pulse. We interpret the first type of behavior as an indication that the wave packet produced by the pump laser is localized in a region of the S 2 potential energy surface where the vertical ionization energy exceeds the probe photon energy, whereas the second type of behavior may be described by a reduced absorption cross section for S 0 → S 2 followed by incoherent decay of the excited molecules. * rjgordon@uic.edu 2