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Molecular polaritons arise when molecules interact so strongly with lightthat they become entangled with each other. This light-matter hybridizationalters the chemical and physical properties of the molecular system and allowschemical reactions to be controlled without the use of external fields. Weinvestigate the impact of strong light-matter coupling on the electronicstructure using perturbative approaches and demonstrate thatRayleigh-Schr\"odinger perturbation theory can reproduce the ground stateenergies in optical cavities to comparable accuracy as ab initio cavity quantumelectrodynamics methodologies for currently relevant coupling strengths. Themethod is effective in both low and high cavity frequency regimes andstraightforward to implement via response functions. Furthermore, we establishsimple relations between cavity-induced intermolecular forces and van der Waalsforces. These findings provide valuable insight into the manipulation ofground-state polaritonic energy landscapes, shedding light on the systems andconditions in which modifications can be achieved.

Understanding the polaritonic ground state in cavity quantum electrodynamics