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Abstract:
The field of polariton chemistry studies molecules strongly coupled to the light field of optical cavities. The resulting modification of the potential energy landscape has been shown to allow control of the chemical and physical properties of materials and molecular ensembles. In this work, we have studied the theoretical description of molecules interacting with the vacuum field of an optical cavity, derived from the Pauli-Fierz Hamiltonian. We extend the molecular Tavis-Cummings model to include coupling terms arising from the static dipole moments that are present in molecules as well as the dipole self-energy. Since this representation complicates the distinction between photon and matter degrees of freedom, a transformation to the coherent state basis is required.
To verify the importance of these additional coupling terms in the molecular model, we simulated the excited state dynamics and spectroscopy of MgH+ molecules resonantly coupled to a cavity vacuum mode. We observe a significant difference in the dynamics when the interaction terms are included individually, compared to a naive molecular Tavis-Cummings model. A reduced effect is obtained when a combined contribution is considered, indicating that considering both terms is essential in the system description. In addition, a strong asymmetry in the spectrum is observed, which can be explained as an influence of the vibrational states and the molecular Franck-Condon factors. To make the analysis of large ensembles computationally accessible, we developed an effective model which is based on a two-level system model.