Real-time evolution of the valence electronic structure in a dissociating molecule.

Time-resolved valence band photoelectron spectroscopy with a temporal resolution of 135 fs is used to map the entire occupied valence electronic structure of photoexcited gas-phase Br2 molecules during dissociation. The observed shifting and mixing of valence energy levels defines a transition period where the system appears to be intermediate between atoms and molecules. The surprisingly short bond breaking or dissociation time is determined by monitoring in real time how the photoelectron multiplet structure of the free atom arises from the valence states of the photoexcited molecule.