A Machine-Driven Hunt for Global Reaction Coordinates of Azobenzene Photoisomerization

摘要

Azobenzene is a very important system that is often studied for better understanding light-activated mechanical transformations via photoisomerization. The central C–N═N–C dihedral angle is widely recognized as the primary reaction coordinate for changing cis- to trans- azobenzene and vice versa. We report on a global reaction coordinate (containing all internal coordinates) to thoroughly describe the reaction mechanism for azobenzene photoisomerization. Our global reaction coordinate includes all of the internal coordinates of azobenzene contributing to the photoisomerization reaction coordinate. We quantify the contribution of each internal coordinate of azobenzene to the overall reaction mechanism. Finally, we provide a detailed mapping on how each significantly contributing internal coordinate changes throughout the energy profile (from trans to transition state and subsequently to cis ). In our results, the central C–N═N–C dihedral remains the primary internal coordinate responsible for the reaction coordinate; however, we also conclude that the disputed inversion-assisted rotation is half as important to the overall reaction mechanism and the inversion-assisted rotation is driven by four adjacent dihedral angles C–C–N═N with very little change to the adjacent C–C–N angles.