Proton Quantization and Vibrational Relaxation in Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer in a Solvated Phenol-Amine Complex

Nonadiabatic dynamics simulations of photoinduced proton-coupled electron transfer (PCET) in a phenol–amine complex in solution were performed. The electronic potential energy surfaces were generated on-the-fly with a hybrid quantum mechanical/molecular mechanical approach that described the solute with a multiconfigurational method in a bath of explicit solvent molecules. The transferring hydrogen nucleus was represented as a quantum mechanical wave function calculated with grid-based methods, and surface hopping trajectories were propagated on the adiabatic electron–proton vibronic surfaces. Following photoexcitation to the excited S₁ electronic state, the overall decay to the ground vibronic state was found to be comprised of relatively fast decay from a lower proton vibrational state of S₁ to a highly excited proton vibrational state of the ground S₀ electronic state, followed by vibrational relaxation within the S₀ state. Proton transfer can occur either on the highly excited proton vibrational states of S₀ due to small environmental fluctuations that shift the delocalized vibrational wave functions or on the low-energy proton vibrational states of S₁ due to solvent reorganization that alters the asymmetry of the proton potential and reduces the proton transfer barrier. The isotope effect arising from replacing the transferring hydrogen with deuterium is predicted to be negligible because hydrogen and deuterium behave similarly in both types of proton transfer processes. Although an isotope effect could be observed for other systems, in general the absence of an isotope effect does not imply the absence of proton transfer in photoinduced PCET systems. This computational approach is applicable to a wide range of other photoinduced PCET processes