Electron Transfer and Solvent-Mediated Electronic Localization in Molecular Photocatalysis

This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born–Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate the electron transfer. We observe how Jahn–Teller distortion effects play out in solution, when the molecule has energetically close-lying states, and how this distortion is averaged out in the thermal sampling. Finally, we demonstrate how the solvent helps stabilize and localize the separated charge. The information on the electronic configuration and separate states is of key importance for designing next-generation photocatalysts.