Department of Chemistry, Duke University, Durham, North Carolina27708, United States.
Department of Chemistry and Department of Physics, Duke University, Durham, North Carolina27708, United States.
J Phys Chem Lett. 2022 Oct 27;13(42):9822-9828. doi: 10.1021/acs.jpclett.2c02496. Epub 2022 Oct 14.
Cavity polaritonics creates novel opportunities to direct chemical reactions. Electron transfer (ET) reactions are among the simplest reactions, and they underpin energy conversion. New strategies to manipulate and direct electron flow at the nanoscale are of particular interest in biochemistry, energy science, bioinspired materials science, and chemistry. We show that optical cavities can modulate electron transfer pathway interferences and ET rates in donor-bridge-acceptor (DBA) systems. We derive the rate for DBA electron transfer when the molecules are coupled to cavity modes, emphasizing novel cavity-induced pathway interferences with the molecular electronic coupling pathways, as these interferences allow a new kind of ET rate tuning. The interference between the cavity-induced coupling pathways and the intrinsic molecular coupling pathway is dependent on the cavity properties. Thus, manipulating the interference between the cavity-induced DA coupling and the bridge-mediated coupling offers an approach to direct and manipulate charge flow at the nanoscale.
腔量子电动力学为定向化学反应创造了新的机会。电子转移（ET）反应是最简单的反应之一，它们是能量转换的基础。在生物化学、能源科学、仿生材料科学和化学中，操纵和定向纳米尺度电子流的新策略尤其受到关注。我们表明，光学腔可以调制供体-桥-受体（DBA）系统中的电子转移途径干扰和 ET 速率。当分子与腔模耦合时，我们推导出 DBA 电子转移的速率，强调了分子电子耦合途径与腔诱导途径干扰的新颖性，因为这些干扰允许一种新的 ET 速率调谐。腔诱导耦合途径与固有分子耦合途径之间的干扰取决于腔的性质。因此，操纵腔诱导的 DA 耦合与桥介导的耦合之间的干扰为在纳米尺度上定向和控制电荷流动提供了一种方法。
