Nonadiabatic molecular dynamics simulations shed light on the timescale of furylfulgide photocyclization
M. Kochman
New Journal of Chemistry, 2024
Abstract
The sequence of events during the photocyclisation of furylfulgides is not fully understood, and there is a significant disparity between ring closing timescales determined with the use of transient absorption spectroscopy [Siewertsen et al., Phys. Chem. Chem. Phys., 2011, 13, 3800] and the timescale estimated on the basis of nonadiabatic molecular dynamics (NAMD) simulations [Kochman et al., Phys. Chem. Chem. Phys., 2022, 24, 18103]. With a view to resolving this issue, in the present study I report NAMD simulations of the photorelaxation process of a model furylfulgide with a bulky alkyl substituent at carbon atom C3. I employed a pattern recognition algorithm in order to automate the analysis of the simulated trajectories. According to the simulation results, the bulky alkyl group causes a substantial increase in the photocyclisation quantum yield, but the timescale of ring closing is only marginally affected. I discuss the implications of these findings in light of the available spectroscopic data.