TY  - JOUR
A1  - Fischer, Eric W.
A1  - Saalfrank, Peter
T1  - Cavity-induced non-adiabatic dynamics and spectroscopy of molecular rovibrational polaritons studied by multi-mode quantum models
T2  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - 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-Perot 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. Published under an exclusive license by AIP Publishing.
Y1  - 2022
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/56298
SN  - 0021-9606
SN  - 1089-7690
VL  - 157
IS  - 3
PB  - American Institute of Physics
CY  - Melville
ER  -