paper

Cavity-induced Non-Adiabatic Dynamics and Spectroscopy of Molecular Rovibrational Polaritons studied by Multi-Mode Quantum Models

arXiv:2205.00945 · doi:10.1063/5.0098006

Abstract

We study theoretically the quantum dynamics and spectroscopy of rovibrational polaritons formed in a model system composed of a single rovibrating diatomic molecule, which interacts with two degenerate, orthogonally polarized modes of an optical Fabry-Pérot cavity. We employ an effective rovibrational Pauli-Fierz Hamiltonian in length gauge representation and identify three-state vibro-polaritonic conical intersections (VPCIs) between singly-excited vibro-polaritonic states in a two-dimensional angular coordinate branching space. The lower and upper vibrational polaritons are of mixed light-matter hybrid character, whereas the intermediate state is purely photonic in nature. The VPCIs provide effective population transfer channels between singly-excited vibrational polaritons, which manifest in rich interference patterns in rotational densities. Spectroscopically, three bright singly-excited states are identified, when an external infrared laser field couples to both a molecular and a cavity mode. The non-trivial VPCI topology manifests as pronounced multi-peak progression in the spectral region of the upper vibrational polariton, which is traced back to the emergence of rovibro-polaritonic light-matter hybrid states. Experimentally ubiquitous spontaneous emission from cavity modes induces a dissipative reduction of intensity and peak broadening, which mainly influences the purely photonic intermediate state peak as well as the rovibro-polaritonic progression.

14 pages, 7 figures; accepted at Journal of Chemical Physics

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