Ultrafast structural dynamics and isomerization in Rydberg-exited Quadricyclane

Rudakov, Fedor M.

doi:10.1063/1.3697472

Ultrafast structural dynamics and isomerization in Rydberg-exited Quadricyclane

Journal Article · Sun Apr 01 00:00:00 EDT 2012 · The Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3697472· OSTI ID:1050309

Rudakov, Fedor M. ^[1]

ORNL

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 {tau}{sub 2} = 136(45) fs. The lifetime of the 3p Rydberg state in quadricyclane is {tau}{sub 1} = 320(31) and the lifetime of the 3s Rydberg state in norbornadiene is {tau}{sub 3} = 394(32).

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1050309

Journal Information:: The Journal of Chemical Physics, Journal Name: The Journal of Chemical Physics Journal Issue: 13 Vol. 136; ISSN JCPSA6; ISSN 0021-9606

Country of Publication:: United States

Language:: English

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