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We present the simulation of the photochemical dynamics of cyclobutanoneinduced by the excitation of the 3s Rydberg state. For this purpose, we applythe complete active space self-consistent field method together with spin-orbitmultireference configuration interaction singles treatment, combined with thetrajectory surface hopping for inclusion of the nonadiabatic effects. Thesimulations were performed in the spin-adiabatic representation including nineelectronic states derived from three singlet and two triplet spin-diabaticstates. Our simulations reproduce the two previously observed primarydissociation channels: the C2 pathway yielding C2H4 + CH2CO and the C3 pathwayproducing c-C3H6 + CO. In addition, two secondary products, CH2 + CO from theC2 pathway and C3H6 from the C3 pathway, both of them previously reported, arealso observed in our simulation. We determine the ratio of the C3:C2 productsto be about 2.8. Our findings show that most of the trajectories reach theirelectronic ground state within 200 fs, with dissociation events finished after300 fs. We also identify the minimum energy conical intersections that areresponsible for the relaxation and provide an analysis of the photochemicalreaction mechanism based on multidimensional scaling. Furthermore, wedemonstrate a minimal impact of triplet states on the photodissociationmechanism within the observed timescale. In order to provide a direct link toexperiments, we simulate the gas phase ultrafast electron diffraction patternsand connect their features to the underlying structural dynamics.

A CASSCF/MRCI Trajectory Surface Hopping Simulation of the Photochemical  Dynamics and the Gas Phase Ultrafast Electron Diffraction Patterns of  Cyclobutanone