标题： 黑暗极化子态在分子电子强耦合中的作用 显示英文标题

标题： The role of dark polariton states for electronic strong coupling in molecules

摘要： 极化子化学研究了通过光学腔中的强光-物质耦合可能对化学和光化学反应的修改，这一点在过去几年中已经通过众多实验得到证明。这些实验通常在假设分子集合仅被单个光子激发的情况下，用Jaynes-Cummings模型或Tavis-Cummings模型来解释。在这样的模型中，两个极化子态与大量的暗态竞争，抑制了熵驱动的极化子反应。我们分析了Tavis-Cummings模型的高激发态，并结合一个类似于光化学反应的三能级系统。我们证明，允许存在多于一个激发会使相关极化子的反应在熵上更加有利。 显示英文摘要

摘要： Polaritonic chemistry investigates the possible modification of chemical and photochemical reactions by means of strong light-matter coupling in optical cavities, as demonstrated in numerous experiments over the last few years. These experiments are typically interpreted in terms of the Jaynes-Cummings or Tavis-Cummings models under the assumption that the molecular ensemble is only excited by a single photon. In such a model, two polariton states compete with an overwhelming number of dark states, inhibiting polaritonic reactions entropically. We analyze the higher excitation manifolds of the Tavis-Cummings model along with a three-level system that resembles photochemical reactions. We demonstrate that allowing for more than a single excitation makes the reaction of the involved polaritons entropically more favorable.