Wellnitz D, Pupillo G, Schachenmayer J
ISIS (UMR 7006), University of Strasbourg and CNRS, and icFRC, 67000 Strasbourg, France.
J Chem Phys. 2021 Feb 7;154(5):054104. doi: 10.1063/5.0037412.
We study a simple model for photoinduced electron transfer reactions for the case of many donor-acceptor pairs that are collectively and homogeneously coupled to a photon mode of a cavity. We describe both coherent and dissipative collective effects resulting from this coupling within the framework of a quantum optics Lindblad master equation. We introduce a method to derive an effective rate equation for electron transfer by adiabatically eliminating donor and acceptor states and the cavity mode. The resulting rate equation is valid for both weak and strong coupling to the cavity mode and describes electronic transfer through both the cavity-coupled bright states and the uncoupled dark states. We derive an analytic expression for the instantaneous electron transfer rate that depends non-trivially on the time-varying number of pairs in the ground state. We find that under proper resonance conditions, and in the presence of an incoherent drive, reaction rates can be enhanced by the cavity. This enhancement persists, and can even be largest, in the weak light-matter coupling regime. We discuss how the cavity effect is relevant for realistic experiments.
我们研究了一个简单的光致电子转移反应模型,适用于多个供体 - 受体对集体且均匀地耦合到腔的光子模式的情况。我们在量子光学林德布拉德主方程的框架内描述了这种耦合产生的相干和耗散集体效应。我们引入了一种方法,通过绝热消除供体和受体状态以及腔模式来推导电子转移的有效速率方程。所得的速率方程对于与腔模式的弱耦合和强耦合均有效,并描述了通过腔耦合亮态和未耦合暗态的电子转移。我们推导了一个瞬时电子转移速率的解析表达式,该表达式非平凡地依赖于基态对的时变数量。我们发现,在适当的共振条件下,并且在存在非相干驱动的情况下,腔可以提高反应速率。这种增强在弱光 - 物质耦合 regime 中持续存在,甚至可能最大。我们讨论了腔效应与实际实验的相关性。