Lineshapes in Pump-Probe Spectroscopy of Polaritons

TL;DR

This study investigates how the spectral lineshapes in pump-probe spectroscopy of polaritons depend on their photonic and molecular character, revealing how relaxation processes can be spectrally distinguished and better understood.

Contribution

It introduces a method to analyze lineshape dependence on polariton character and demonstrates how relaxation to dark states can be spectrally resolved through phase flips.

Findings

Lineshape varies with photonic/molecular ratio

Relaxation to dark states causes a phase flip in signals

Spectral signatures can disentangle different polariton effects

Abstract

Forming new hybrid quasiparticles by strong light-matter coupling is a promising tool for tailoring photophysics and photochemistry of molecules. Thus, the ultrafast dynamics of polaritons formed upon strong light-matter coupling has been extensively studied by pump-probe spectroscopy. Although it was predicted that the partial photonic character of polaritons should shorten their lifetime compared to purely molecular excited states, many studies do not observe this effect. So far, the unexpected longevity of the spectral signatures was either explained by relaxation into a manifold of so-called dark states or by other uncontrolled effects that change the properties of cavity materials. In order to resolve these issues, we investigate here the dependence of the lineshape of pump-probe spectra of polaritons on the ratio of photonic and molecular character. Furthermore, by phenomenologically including relaxation to dark states, we find that it is possible to spectrally resolve this relaxation process by observing a characteristic phase flip in the pump-probe signal. Our results show that the signatures of various effects and their contributions to the polariton dynamics can be disentangled from the spectral lineshapes.