title: Ultrafast structural and isomerization dynamics in the Rydberg-exited quadricyclane: norbornadiene system.
abstract: The quadricyclane-norbornadiene system is an important model for the isomerization dynamics between highly strained molecules. In a breakthrough observation for a polyatomic molecular system of that complexity, we follow the photoionization from Rydberg states in the time-domain to derive a measure for the time-dependent structural dynamics and the time-evolving structural dispersion even while the molecule is crossing electronic surfaces. The photoexcitation to the 3s and 3p Rydberg states deposits significant amounts of energy into vibrational motions. We observe the formation and evolution of the vibrational wavepacket on the Rydberg surface and the internal conversion from the 3p Rydberg states to the 3s state. In that state, quadricyclane isomerizes to norbornadiene with a time constant of τ(2) = 136(45) fs. The lifetime of the 3p Rydberg state in quadricyclane is τ(1) = 320(31) and the lifetime of the 3s Rydberg state in norbornadiene is τ(3) = 394(32).
authors.affiliation: Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37931, USA. rudakovfm@ornl.gov
authors.forename: Fedor
authors.initials: F
authors.lastname: Rudakov
authors.forename: Peter M
authors.initials: PM
authors.lastname: Weber