Borges Lucas, Schnappinger Thomas, Kowalewski Markus
Department of Physics, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm, Sweden.
J Phys Chem Lett. 2025 Aug 7;16(31):7807-7815. doi: 10.1021/acs.jpclett.5c01480. Epub 2025 Jul 25.
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 past 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.
极化激元化学研究通过光学腔中强光与物质的耦合对化学反应和光化学反应进行可能的改性，过去几年的大量实验已证明了这一点。这些实验通常根据Jaynes-Cummings或Tavis-Cummings模型进行解释，其假设分子系综仅由单个光子激发。在这样的模型中，两个极化激元态与大量暗态竞争，从熵的角度抑制了极化激元反应。我们分析了Tavis-Cummings模型的高激发流形以及一个类似于光化学反应的三能级系统。我们证明，允许不止一个激发使得所涉及的极化激元的反应在熵上更有利。
