Cavity-induced non-adiabatic dynamics and spectroscopy of molecular rovibrational polaritons studied by multi-mode quantum models
Cavity-induced non-adiabatic dynamics and spectroscopy of molecular rovibrational polaritons studied by multi-mode quantum models
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DOI：
10.1063/5.0098006
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发表时间：
2022-07-21
影响因子：
4.4
通讯作者：
Saalfrank, Peter
中科院分区：
文献类型：
--
作者：
Fischer, Eric W.;Saalfrank, Peter
本文从理论上研究了由单个振转双原子分子组成的模型系统中振转极化激元的量子动力学和光谱学。我们采用一个有效的转振Pauli-Fierz哈密顿长度规范表示和识别三个国家的振动极化激元锥形交叉点（VPCI）之间的单激发振动极化激元状态在二维角坐标分支空间。上下振动极化激元具有混合光-物质杂化特性，而中间态则具有纯光子性质。VPCI提供了单激发振动极化激元之间有效的布居转移通道，在转动密度中表现出丰富的干涉图样。光谱上，三个明亮的单激发态时，外部红外激光场耦合到一个分子和一个腔模式被确定。非平凡的VPCI拓扑表现为显着的多峰进展中的光谱区域的上振动极化激元，这可以追溯到出现的光振动极化激元光物质混合态。实验上，腔模的普遍自发辐射导致了强度的耗散降低和峰展宽，主要影响纯光子中间态峰以及振子-极化激元过程。由AIP Publishing独家授权出版。
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.