The thermal helix inversion (THI) of the overcrowded-alkene-based molecular motors determines the speed of the unidirectional rotation due to the high reaction barrier in the ground state, in comparison with the ultrafast photo-reaction process. Recently, a phosphine-based motor has achieved all-photochemical rotation experimentally, promising to be controlled without thermal step. However, the mechanism of this photochemical reaction has not been fully revealed. The comprehensive computational studies on photoisomerization still resort to nonadiabatic molecular dynamics (NAMD) simulations based on electronic structure calculations, which remains a high computational cost for large systems like molecular motors. Machine learning (ML) has become an accelerating tool in NAMD simulations recently, where excited-state potential energy surfaces are constructed analytically with high accuracy, providing an efficient approach for simulations in photochemistry. Herein the reaction pathway is explored by a spinflip time-dependent density functional theory (SF-TDDFT) approach in combination with ML-based NAMD simulations. According to our computational simulations, we notice one of the key factors of fulfilling all-photochemical rotation in the phosphinebased motor is that the excitation energies of four isomers are similar. Additionally, a shortcut photo-induced transformation between unstable isomers replaces the THI step, which shares the conical intersection (CI) with photoisomerization. In this study, we provide a practical approach to speed up the NAMD simulations in photochemical reactions for a large system, which could be extended to other complex systems.
supporting Information of relevant data
The supporting Information contain geometrical parameters definition, energy profile, k-fold cross validation, statistical analysis of trajectories, electronic state populations, simulated absorption spectrum, molecular orbitals, comparison between optimized configurations and experimental X-ray structures, relative energy, and cartesian coordinates of optimized configurations (PDF).
video of trajectories
Typical trajectories in the photoisomerization (mp4).