Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois, USA.
J Phys Chem B. 2013 Jan 31;117(4):1010-20. doi: 10.1021/jp3102942. Epub 2013 Jan 15.
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.
我们研究了一个四级系统中的量子干涉效应，这个系统可以作为一个最小模型来理解从合成分子结构到光系统-1 反应中心等系统中的这种行为。我们研究了几种退相干过程对电子转移速率的影响。退相干幅度的速率函数表现出了预期的 Kramer 翻转。然而，不同的退相干过程对量子干涉的影响不同。研究表明，当桥接位点没有去相位时，超交换转移会通过建设性量子干涉得到增强。桥接位点的去相位为快速电子转移打开了（经典的）扩散通道，这会主导超交换电流并减少建设性量子干涉。
