It remains unclear how the collective strong coupling of cavity-confined photons to the electronic transitions of molecular chromophore leverages the distinct properties of the polaritonic constituents for future technologies. In this study, we design, fabricate, and characterize multiple types of Fabry-Pérot (FP) mirco-resonators containing copper(II) tetraphenyl porphyrin (CuTPP) to show how cavity polariton formation affects radiative relaxation processes in the presence of substantial non-Condon vibronic coupling between two of this molecule’s excited electronic states. Unlike the prototypical enhancement of Q state radiative relaxation of CuTPP in a FP resonator incapable of forming polaritons, we find the light emission processes in multimode cavity polariton samples become enhanced for cavity-exciton energy differences near those of vibrations known to mediate non-Condon vibronic coupling. We propose the value of this detuning is consistent with radiative relaxation of Herzberg-Teller polaritons into collective molecular states coupled to the cavity photon coherently. We contrast the feature stemming from light emission from the HT polariton state with those that occur due to polariton-enhanced light absorption. Our results demonstrate the landscape of molecular and photonic interactions enabled by cavity polariton formation using complex chromophores and how researchers can design resonators to leverage these interactions to characterize and control polaritonic properties.

中文翻译：

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解读多模卟啉腔极化子样品中增强光发射和吸收之间的关系

目前尚不清楚空腔限制光子与分子发色团的电子跃迁的集体强耦合如何利用极化子成分的独特性质来实现未来技术。在这项研究中，我们设计、制造和表征了多种类型的含有铜（II）四苯基卟啉（CuTPP）的法布里-珀罗（FP）微谐振器，以展示空腔极化子的形成如何在存在大量非辐射的情况下影响辐射弛豫过程。该分子的两个激发电子态之间的康顿电子振动耦合。与不能形成极化子的 FP 谐振器中 CuTPP Q 态辐射弛豫的典型增强不同，我们发现多模腔极化子样品中的光发射过程因腔激子能量差异而增强，接近已知介导非康顿电子振动的振动能量差异耦合。我们提出这种失谐的值与赫兹伯格-泰勒极化激元辐射弛豫成与腔光子相干耦合的集体分子态一致。我们将 HT 极化子态的光发射所产生的特征与极化子增强的光吸收所产生的特征进行了对比。我们的结果展示了通过使用复杂发色团形成空腔极化子而实现的分子和光子相互作用的景观，以及研究人员如何设计谐振器以利用这些相互作用来表征和控制极化子特性。