New insights into the photocyclization reaction of a popular diarylethene switch: a nonadiabatic molecular dynamics study

Diarylethene (DAE) molecular switches have continued to attract the attention of researchers for over 20 years. Their remarkable photophysical properties endow them with countless applications in photonics and molecular technologies. However, despite extensive experimental and theoretical research, the mechanism of DAE photoswitching is not yet fully rationalized. In this work, we investigate the ring closure dynamics of a popular DAE switch, 1,2-bis(3-methyl-5-phenyl-2 thienyl)perfluorocyclopentene (PT), using nonadiabatic molecular dynamics (NAMD) simulations. Employing the fewest switches surface hopping protocol, along with the semi-empirical multireference ODM2/MRCI-SD method, we investigate possible reaction pathways for this photoprocess, as well as their timescales and resulting photoproducts. Furthermore, using a dynamic configuration-space sampling procedure, we elucidate the role of triplet states in the photocyclization of PT, supporting available experimental data for the closely related DMPT molecule, which indicate an ultrafast intersystem crossing (ISC) transition competing with the singlet-driven photoswitching reaction. Our findings not only corroborate experimental studies on DAE switches, but also provide new mechanistic insights into the potential use in the rational design of DAE switches tailored for specific technological applications.