Non-Markovian quantum-classical ratchet for ultrafast long-range electron-hole separation in condensed phases

Abstract

In organic photovoltaic systems, a photogenerated molecular exciton in the donor domain dissociates into a hole and an electron at the donor/acceptor heterojunction, and subsequently separate into free charge carriers that can be extracted as photocurrents. The recombination of the once-separated electron and hole is a major loss mechanism in photovoltaic systems, which controls their performance. Hence, efficient photovoltaic systems need built-in ratchet mechanisms, namely, ultrafast charge separation and retarded charge recombination. In order to obtain insight into the internal working of the experimentally observed ultrafast long-range charge separation and protection against charge recombination, we theoretically investigate a potential ratchet mechanism arising from the combination of quantum delocalization and its destruction by performing numerically accurate quantum-dynamics calculations on a model system. It is demonstrated that the non-Markovian effect originating from the slow polaron formation strongly suppresses the electron transfer reaction back to the interfacial charge-transfer state stabilized at the donor/accepter interface and that it plays a critical role in maintaining the long-range electron--hole separation.

arXiv comment5 pages, 3 figures, minor revision

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• Insights into photosynthetic energy transfer gained from free-energy structure: Coherent transport, incoherent hopping, and vibrational assistance revisited
• Control of Quantum Dynamics of Electron Transfer in Molecular Loop Structures: Spontaneous Breaking of Chiral Symmetry under Strong Decoherence
• Exciton Dissociation and Charge Separation at Donor-Acceptor Interfaces from Quantum-Classical Dynamics Simulations
• Exact description of excitonic dynamics in molecular aggregates weakly driven by light
• Two-dimensional fluorescence spectroscopy with quantum entangled photons and time- and frequency-resolved two-photon coincidence detection