The Interplay between Disorder, Local Relaxation and Collective Behaviors for an ensemble of emitters outside vs inside cavity

TL;DR

This paper investigates how static and dynamic disorder affect collective optical responses of molecular ensembles inside and outside a cavity, revealing disorder's impact on spectral features and molecular processes.

Contribution

It introduces a comprehensive model analyzing the effects of various disorders on collective behaviors in cavity and non-cavity environments, highlighting the differential impact of static versus dynamic disorder.

Findings

Disorder reduces the effective number of molecules contributing to collective response.

Static disorder more strongly disrupts collective behavior than dynamic disorder.

Disorder causes Rabi splitting contraction, especially with orientational disorder.

Abstract

The interplay between collective optical response and molecular static and dynamic disorder is studied using simple effective Hamiltonians for an ensemble of two-level emitters inside and outside a single-mode cavity. We model environmental disorder by randomly modulating the molecular transition frequencies and the coupling between the emitters and the electromagnetic field. We also consider effects of intermolecular interactions and orientational disorder. We investigate how these effects lead to new features in the steady state absorption (outside the cavity), transmission spectra (inside the cavity) and the yield of local molecular processes such as a unimolecular reaction. Outside the cavity, the collective behavior is manifested in the linewidth of the steady state absorption, the emission spectrum, and the local chemical yield. Inside the cavity, however, the collective behavior primarily determines the Rabi splitting. Effects of intermolecular interactions under orientational disorder are also studied. For the most part, for all types of disorder, if we increase disorder, we find a reduction in the collective nature of the molecular response (smaller effective N), and therefore, the Rabi splitting contraction occurs with orientational disorder. Moreover, we find that static disorder is more destructive to collective behavior than dynamic disorder.