Photoinduced Electron Transfer in Donor-Acceptor Complexes: Isotope Effect and Dynamic Symmetry Breaking
| Autor: | Francesco Buda, Huub J. M. de Groot, Jan Paul Menzel |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Physics
Angular momentum Letter 010405 organic chemistry Relaxation (NMR) 010402 general chemistry 01 natural sciences Molecular physics Photoinduced electron transfer 0104 chemical sciences Vibronic coupling Dipole Electron transfer General Materials Science Symmetry breaking Physical and Theoretical Chemistry Physics::Chemical Physics Adiabatic process |
| Zdroj: | Journal of Physical Chemistry Letters Journal of Physical Chemistry Letters, 10, 6504-6511 The Journal of Physical Chemistry Letters |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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