LAUSR

Abstract In view of the considerably high activation energy barrier of the O−O bond formation photocatalytic step in water oxidation, it is essential to understand if and how nonadiabatic factors can accelerate the proton‐coupled electron transfer (PCET) rate in this process to find rational design strategies facilitating this step. Herein, constrained ab initio molecular dynamics simulations are performed to investigate this rate‐limiting step in a series of catalyst‐dye supramolecular complexes functionalized with different alkyl groups on the catalyst component. These structural modifications lead to tunable thermodynamic driving forces, PCET rates, and vibronic coupling with specific resonant torsional modes. These results reveal that such resonant coupling between electronic and nuclear motions contributes to crossing catalytic barriers in PCET reactions by enabling semiclassical coherent conversion of a reactant into a product. Our results provide insight on how to engineer efficient catalyst‐dye supramolecular complexes by functionalization with steric substituents for high‐performance dye‐sensitized photoelectrochemical cells.