Diffractive imaging of dissociation and ground-state dynamics in a complex molecule

We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules (C₂F₄I₂) in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p⊥ orbital to a mixed 5p∥σ hole and CF₂^• antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C₂F₄I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs.