Unveiling the Dance of Molecules: Ro-Vibrational Dynamics of Molecules under Intense Illumination at Complex Plasmonic Interfaces

TL;DR

This paper presents a comprehensive model for simulating the quantum ro-vibrational dynamics of molecules in resonant optical cavities, revealing new relaxation mechanisms and spectral modifications due to strong light-matter coupling.

Contribution

It introduces a novel self-consistent numerical approach for three-dimensional simulations of molecule-cavity interactions, uncovering previously unknown relaxation stabilization effects.

Findings

Modified relaxation pathways inside cavities compared to free space

Persistent molecular alignment from cavity-induced rotational pumping

Altered circular dichroism spectra in chiral metasurfaces

Abstract

Understanding the quantum dynamics of strongly coupled molecule-cavity systems remains a significant challenge in molecular polaritonics. This work develops a comprehensive self-consistent model simulating electromagnetic interactions of diatomic molecules with quantum ro-vibrational degrees of freedom in resonant optical cavities. The approach employs an efficient numerical methodology to solve coupled Schrodinger-Maxwell equations in real space-time, enabling three-dimensional simulations through a novel molecular mapping technique. The study investigates relaxation dynamics of an ensemble of molecules following intense resonant pump excitation in Fabry-Perot cavities and at three-dimensional plasmonic metasurfaces. The simulations reveal dramatically modified relaxation pathways inside cavities compared to free space, characterized by persistent molecular alignment arising from cavity-induced rotational pumping. They also indicate the presence of a previously unreported relaxation stabilization mechanism driven by dephasing of the collective molecular-cavity mode. Additionally, the study demonstrates that strong molecular coupling significantly modifies the circular dichroism spectra of chiral metasurfaces, suggesting new opportunities for controlling light-matter interactions in quantum optical systems.