Abstract
When a stable negative ion is similar in structure to the transition state for the neutral reaction, photodetachment of the anion can be used to directly access the transition state region of the neutral potential energy surface. In this work, from the theoretical side, we address the femtosecond time-resolved experiment for the cyclooctatetraene (COT) unimolecular reaction which has been previously performed by Zewail et al. (2004), where the time-evolution of the nuclear wave packet, which is initially localized around the transition state region via instantaneous photodetachment, is monitored by an ionization laser. The oscillatory behavior of the ionization efficiency observed in their experiment is analyzed in detail using both the reduced-dimensionality quantum dynamics calculations and full-dimensional direct dynamics calculations on the CASSCF-level potential energy surfaces. We found that the behavior observed in an early stage can be attributable to the ring-inversion dynamics of COT.
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