Decoherence and quantum interference in a four-site model system: Mechanisms and turnovers

We study quantum interference effects in a four-level system which can be used as a minimal model to understand such behavior in systems from synthetic molecular structures to the photosystem-1 reaction center. The effects of environmental decoherence and relaxation on the electron transfer rate are investigated for several types of decoherence processes. The rate as a function of decoherence amplitude shows Kramers turnover, as expected. However, various decoherence processes affect the quantum interference differently. It is shown that when the bridge sites are not dephased the superexchange transfer is enhanced by constructive quantum interference. Dephasing on bridge sites opens a (classical) diffusive channel for fast electron transfer, which can dominate the superexchange current and reduce the constructive quantum interference.