Collective response in light-matter interactions: The interplay between strong coupling and local dynamics

TL;DR

This paper investigates how collective light-matter interactions influence molecular nuclear dynamics in optical cavities, revealing that local nuclear responses dominate over collective polaron decoupling effects in the studied model.

Contribution

It introduces a simplified Holstein-Tavis-Cummings model to analyze the interplay between collective optical responses and local nuclear dynamics in strong coupling regimes.

Findings

Dynamics mostly reflect local nuclear configurations

Polaron decoupling is not the dominant effect

Model captures short-time and driven responses

Abstract

A model designed to mimic the implications of the collective optical response of molecular ensembles in optical cavities on molecular vibronic dynamics is investigated. Strong molecule-radiation field coupling is often reached when a large number N of molecules respond collectively to the radiation field. In electronic strong coupling, molecular nuclear dynamics following polariton excitation reflects (a) the timescale separation between the fast electronic and photonic dynamics and the slow nuclear motion on one hand, and (b) the interplay between the collective nature of the molecule-field coupling and the local nature of the molecules nuclear response on the other. The first implies that the electronic excitation takes place, in the spirit of the Born approximation, at an approximately fixed nuclear configuration. The second can be rephrased as the intriguing question, can the collective nature of the optical excitation lead to collective nuclear motion following polariton formation, resulting in so-called polaron decoupled dynamics. We address this issue by studying the dynamical properties of a simplified Holstein-Tavis-Cummings type model, in which boson modes representing molecular vibrations are replaced by two-level systems while the boson frequency and the vibronic coupling are represented by the coupling between these levels (that induces Rabi oscillations between them) and electronic state dependence of this coupling. We investigate the short-time behavior of this model following polariton excitation as well as its response to CW driving and its density of states spectrum. We find that, while some aspects of the dynamical behavior appear to adhere to the polaron decoupling picture, the observed dynamics mostly reflect the local nature of the nuclear configuration of the electronic polariton rather than this picture.