Nonadiabatic Dynamics Simulations on Early-Time Photochemistry of Spirobenzopyran.

Abstract

Photoinduced ring-opening, decay, and isomerization of spirobenzopyran have been explored by the OM2/MRCI nonadiabatic dynamics simulations based on Tully's fewest-switches surface hopping scheme. The efficient S1 to S0 internal conversion as observed in experiments is attributed to the existence of two efficient excited-state decay pathways. The first one is related to the C-N dissociation, and the second one is done to the C-O dissociation. The C-O dissociation pathway is dominant, and more than 90% trajectories decay to the S0 state via the C-O bond-fission related S1/S0 conical intersections. Near these regions in the S0 state, trajectories can either return to spirobenzopyran or proceed to various intermediates including merocyanine via a series of bond rotations. Our nonadiabatic dynamics simulations also demonstrate that the hydrogen-out-of-plane (HOOP) motion is important for efficient and ultrafast excited-state deactivation. On the other hand, we have also found that the replacement of methyl groups by hydrogen atoms in spirobenzopyran can artificially introduce different intramolecular hydrogen transfers leading to hydrogen-transferred intermediates. This finding is important for the community and demonstrates that such a kind of structural truncation, sometimes, could be problematic, leading to incorrect photodynamics. Our present work provides valuable insights into the photodynamics of spirobenzopyran, which could be helpful for the design of spiropyran-based photochromic materials.