Cartoon of the experimental approach: The experiment starts with a shaped UV pulse interacting with the molecule initially in the CHD conformation (a). Following UV excitation it evolves toward a CI (b) after which it can become CHD again (c) or undergo ring opening to become HT (e). Subsequent IR ionization leads to pronounced differences in the TOFMS for the two isomers (d) and (f). The geometries shown were derived by ab initio calculations and the two TOFMSs were measured on raw samples and presented here on the same vertical scale. Carbon atoms and are labeled in appropriate panels.
Circles and lines: MCQDPT2(8,10) calculation of the lowest five energy levels of for a relaxed potential energy scan along the bond length. Squares: energies of and at the equilibrium geometries of the neutral CHD (left side) and HT (right side), respectively. Crosses: five lowest energy levels for the cation at the geometries corresponding to the CIs in the neutral.
and parent ion yields as a function of pump-probe delay. The signals are individually normalized to their maximum values.
Top panel: peak integrals with the unshaped and the shaped pulse (UV background subtracted). Bottom panel: shaped/unshaped peak integral ratios.
Top panel: Spectral phases and corresponding spectral intensities of two of the optimal pulses found by the GA. Bottom panel: temporal phases and intensities for the same two pulses. Black lines represent the results of a GA run at full intensity, while the red lines represent the results of a run at 20% of this intensity. Solid lines are used for intensities while dashed lines are used for the phases.
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