Assessing the Determinants of Cavity Polariton Relaxation Using Angle-Resolved Photoluminescence Excitation Spectroscopy

The strong coupling of light and matter within electromagnetic resonators leads to the formation of cavity polaritons whose hybrid nature may help certain ground and excited state chemical processes. To help enable the development of polariton chemistry, we have developed and applied a spectroscopic technique to leverage the relatively larger spatial coherence of polaritons to assess the determinants of relaxation in hybrid light–matter states. By exciting the lower polariton (LP) state in cavity samples filled with different metalloporphyrin chromophores, we measured and modeled angle-resolved photoluminescence excitation spectra. Our results suggest that the shortest lived constituent of the LP state characterized by specific Hopfield coefficients limits the light absorption of the intracavity molecules, which we equate with the effective polariton lifetime. Our results suggest that researchers need to consider the lifetimes of both photons and excitons participating in strong light–matter coupling when designing polaritonic systems and the methods they can use to assess the relaxation of polaritonic states.