Ultrafast Photoisomerization of N-(2-Methoxybenzylidene)aniline: Nonadiabatic Surface-Hopping Study

We investigated the ultrafast photoisomerization of N-(2-methoxybenzylidene)aniline in the gas phase excited into the second singlet (S₂) state by nonadiabatic surface-hopping dynamics calculations. Two trans isomers (1E and 1E') were taken into consideration in our dynamics simulation. Three conical intersections (CIs) were characterized in the optimization. The CI between S₂ and the first singlet (S₁) states presents a nearly planar structure, while the other two CIs (CI_twist-I and CI_twist-II) between S₁ and the ground (S₀) states show nearly perpendicular geometries. After two trans isomers excited to the S₂ state, the torsion of the C-N bond connected the phenyl group and the stretch of the central bridging bond make the molecule reach CI_planar, and the S₂/S₁ hopping occurs. During the S₁-state dynamics, the molecule moves to a S₁/S₀ CI (CI_twist-I or CI_twist-II) by the rotation of the central bridging bond. The cis isomer is obtained through a barrierless pathway in the S₀ state with the torsion of the three bridging bonds. There is a main channel and an alternative one for the photoisomerization process of both trans isomers. CI_twist-I and CI_twist-II act as S₁/S₀ decay funnels in the main isomerization channels of 1E and 1E' isomers, respectively, and the photochemical processes of 1E and 1E' lead to different cis isomers.