Efficient Photochemical Merocyanine-to-Spiropyran Ring Closure Mechanism through an Extended Conical Intersection Seam. A Model CASSCF/CASPT2 Study

Abstract

A mechanism of the thermal and photochemical bleaching of merocyanine to spiropyran is proposed on the basis of CASSCF/CASPT2 calculations on the 6-(2-propenyliden)cyclohexadienone model system. Our results suggest that this photochemical transformation takes place in two steps. First, the initially pumped 1(pi-pi) S2 undergoes radiationless decay to 1(n-pi) S1 via an extended S2/S1 conical intersection seam that runs approximately parallel to the trans-to-cis isomerization coordinate, a few kilocalories per mole higher in energy. Thus, S2 --> S1 internal conversion is possible at all values of the S2 trans-to-cis reaction coordinate. Second, on the S1 potential energy surface, there is a barrierless ring closure reaction path from the S1 cis minimum that leads to a peaked S1/S0 conical intersection where the deactivation to the ground state takes place. The inertia of the moving nuclei then drives the system toward the ground-state minimum of the 2H-chromene product. Thus, the extended seam topology of the S2/S1 conical intersection and the coordinate of the branching space of the S1/S0 conical intersection are essential to explain the efficiency and high speed of this reaction.