Polaritonic Coupled Cluster Theory for Unpolarized Cavities Exploiting Point-Group Symmetry

Abstract

We introduce a generalization of the quantum electrodynamic coupled cluster (QED-CC) wave function ansatz, to describe the strongly coupled light-matter system in an unpolarized optical Fabry-Pérot cavity. This is achieved by explicitly treating two cavity modes in our calculation with perpendicular polarizations and demonstrate that this ansatz preserves the symmetry of an unpolarized cavity. Furthermore, exploiting point-group symmetry enables the assignment of polaritonic excited states as well as their targeted calculation. Using our implementation, the aromatic species benzene, fluorobenzene, and azulene are investigated. We demonstrate that molecules in unpolarized cavities have a complicated excited-state landscapes with a plethora of avoided-crossings. We compare the results for a cavity with a single polarization to those of an unpolarized cavity described by two perpendicular polarization vectors using the excited states of the H2 molecule as an example.