On the FCNS ⇄ FC(NS) reaction: A matrix isolation and theoretical study

The FCNS ⇄ FC(NS) photoisomerization process is a simple model system for molecular switches. Here, we examined the switching processes by experimental and theoretical methods. Prior matrix-isolation IR spectroscopic studies were complemented by matrix-isolation UV spectroscopic measurements to assist the interpretation of the mechanism of the ring closure and opening processes and to verify the accuracy of the computations on the vertical excitation energies. Vertical excitation energies were computed by the EOMEE-CCSD, MCSCF, and MR-CISD methods. Conical intersections were also searched for and three conical intersections along the reaction path FCNS → FC(NS) were located, one conical intersection between the 2A′ and 1A″ state, one between the 1A″ and 1A′ state and one where all three states intersect. The ring opening and closing processes were simulated by non-adiabatic dynamics propagation with the trajectory surface hopping method. The combined computational and experimental results suggest that upon 365 nm irradiation the ring closure FCNS → FC(NS) occurs under participation of all three conical intersections, while 254 nm irradiation causes ring opening FC(NS) → FCNS. Both processes, especially the ring opening, are accompanied by fragmentation into FCN+S.