Impact of Early Coherences on the Control of Ultrafast Photodissociation Reactions

By coherent control, the yield of photodissociation reactions can be maximized, starting in a suitable superposition of vibrational states. In ultrafast processes, the interfering pathways are born from the early vibrational coherences in the ground electronic potential. We interpret their effect from a purely classical picture, in which the correlation between the initial position and momentum helps to synchronize the vibrational dynamics at the Franck-Condon window when the pulse is at its maximum intensity. In the quantum domain, we show that this localization in time and space is mediated by dynamic squeezing of the wave packet.