Photoinduced Electron Transfer in Donor–Acceptor Complexes: Isotope Effect and Dynamic Symmetry Breaking

[Image: see text] Electron–nuclear (vibronic) coupling has emerged as an important factor in determining the efficiency of energy transfer and charge separation in natural and artificial photosynthetic systems. Here we investigate the photoinduced charge-transfer process in a hydrogen-bonded donor–acceptor molecular complex. By using real-time quantum–classical simulations based on time-dependent Kohn–Sham equations, we follow in detail the relaxation from the Franck–Condon point to the region of strong nonadiabatic coupling where electron transfer occurs. We elucidate how the charge transfer is coupled to specific vibrational modes and how it is affected by isotope substitution. The importance of resonance in nuclear and electron dynamics and the role of dynamic symmetry breaking are emphasized. Using the dipole moment as a descriptive parameter, exchange of angular momentum between nuclear and electronic subsystems in an electron–nuclear resonant process is inferred. The performed simulations support a nonadiabatic conversion via adiabatic passage process that was recently put forward. These results are relevant in deriving rational design principles for solar-to-fuel conversion devices.