First principles simulation of the collective rovibronic ground state in a cavity

Abstract

Strong light-matter coupling in Fabry-Perot cavities can modify ground-state molecular reactivity, charge and energy transport, while modifications to single-molecule properties have not been observed experimentally. The mechanisms and reproducibility of such effects remain contested, with conflicting theoretical predictions driven by differences in Hamiltonian choice and quantum state representation. Here, we resolve these ambiguities with numerically exact quantum simulations of cavity-coupled molecular ensembles based on the ab initio light-matter Hamiltonian, treating electrons, nuclei, and cavity photons on equal footing. We investigate ensembles of the rotational-vibrational-electronic Shin-Metiu model using variational tree-tensor-network quantum dynamics, capturing rovibronic couplings and anharmonicity. Embedding ensembles in a cavity induces local modifications of rotational, nuclear, and --more weakly-- electronic observables in individual molecules. The extent of these modifications depends only on the per-molecule coupling strength up until each molecule reaches the ultrastrong coupling regime, which remains unattainable in practical Fabry-Perot setups. Increasing ensemble size toward the thermodynamic limit causes these local modifications to vanish regardless of dipole self-energy inclusion. Nonetheless, global ground-state observables, such as light-matter coupling energy contributions (affecting overall polarizability) and cavity field displacement fluctuations, depend crucially on proper treatment of intermolecular and light-matter correlations, whereas intramolecular observables remain largely insensitive. These insights are crucial for guiding future investigations using approximate quantum treatments, and for the interpretation of experimental results in polaritonic chemistry.