Nonadiabatic molecular dynamics simulations for ultrafast photo-induced ring-opening and isomerization reactions of 2,2-diphenyl-2H-chromene

Abstract

Nonadiabatic molecular dynamics simulations with a global switching algorithm have been performed at the TD-CAM-B3LYP-D3/def2-SVP level of theory for ultrafast photo-induced ring-opening and isomerization reactions upon S₁ excitation for 2,2-diphenyl-2H-chromene (DPC). Both DPC-T and DPC-C conformers undergo ring-opening relaxation and isomerization pathways accompanied with pyran conformation conserved and converted on the S₁ or S₀ states via competition and cooperation between C–O bond dissociation and pyran inversion motions. Upon S₁ excitation, the DPC-T mainly relaxes to the T-type conical intersection region and thus yields a higher ring-opening efficiency with a faster S₁ decay and intermediate formation than those of the DPC-C mainly relaxing to C-type conical intersection. The simulated ring-opening quantum yield for DPC-T (DPC-C) is 0.91 (0.76), which is in good agreement with the experimental value of 0.7–0.9, and the thermal weight averaged lifetimes are estimated as 182.0 fs, 228.6 fs, and 1262.4 fs for the excited-state decay, intermediate formation, and ring-opening product, respectively. These time constants are in good agreement with the experimentally measured τ₁ time constant of 190–450 fs and τ₂ time constant of 1000–1800 fs. The present work could be a valuable reference for understanding the nature of the photorelaxation mechanisms of DPC, and could help to develop DPC-based photoresponsive materials.