Interplay between disorder, local relaxation, and collective behavior for an ensemble of emitters outside versus inside a cavity
Zeyu Zhou, Hsing-Ta Chen, Joseph E. Subotnik, Abraham Nitzan
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 the 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. The 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.