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

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.