DOE OSTI2019
While the ring-opening reaction of 1,3-cyclohexadiene upon excitation to the 1B state has been extensively studied, little is known about the reaction dynamics when exciting higher-lying states. The complexity of the potential energy surfaces found in computational studies suggests that the reaction outcome may depend sensitively on the excitation wavelength and the initially prepared electronic state. We explore the photo-induced kinetics of 1,3-cyclohexadiene upon excitation at 200 nm to the 3p state by ultrafast time-resolved, gas-phase X-ray scattering using the Linac Coherent Light Source (LCLS). Analysis of the experimental scattering data, particularly with respect to the anisotropy, and comparison to ab-initio calculations reveals that the excitation leads dominantly to the 3px and 3py Rydberg electronic states, which relax to the ground state with a time constant of 208 ±11 fs. Unlike in the conventional photochemically induced conrotatory electrocyclic reaction observed at lower excitation energies, at 200 nm the majority of the molecules (76 ± 3%) relax to vibrationally hot cyclohexadiene in the ground electronic state. Furthermore, the photoexcitation activates the reaction on the ground electronic state surface. An equilibrium between the hot cyclohexadiene and 1,3,5-hexatriene is reached by a thermal reaction, giving rates for the forward and backward reaction of 174 ±13 ps and 355 ±45 ps, respectively. The scattering pattern of the final hexatriene product reveals a thermal distribution of rotamers about the carbon-carbon single bonds. The rapid decay of the initially excited state back into the ring-closed form allows us to observe a ground state chemical reaction using ultrafast X-ray scattering.
74 ATOMIC AND MOLECULAR PHYSICS↗