Numerically Exact Solution for a Real Polaritonic System under Vibrational Strong Coupling in Thermodynamic Equilibrium: Loss of Light-Matter Entanglement and Enhanced Fluctuations.

The first numerically exact simulation of a full ab initio molecular quantum system (HD) under strong ro-vibrational coupling to a quantized optical cavity mode in thermal equilibrium is presented. Theoretical challenges in describing strongly coupled systems of mixed quantum statistics (bosons and Fermions) are discussed and circumvented by the specific choice of our molecular system. Our numerically exact simulations highlight the absence of zero temperature for the strongly coupled matter and light subsystems, due to cavity-induced noncanonical conditions. Furthermore, we explore the temperature dependency of light-matter quantum entanglement, which emerges for the ground state but is quickly lost already in the deep cryogenic regime. This is in contrast to predictions from the Jaynes-Cummings model, which is the standard starting point to model collective strong-coupling chemistry phenomenologically. Moreover, we find that the fluctuations of matter remain modified by the quantum nature of the thermal and vacuum-field fluctuations for significant temperatures, e.g., at ambient conditions. These observations (loss of entanglement and coupling to quantum fluctuations) have implications for the understanding and control of polaritonic chemistry and materials science, since a semiclassical theoretical description of light-matter interaction becomes reasonable, but the typical (classical) canonical equilibrium assumption for the nuclear subsystem remains violated. This opens the door for quantum fluctuation-induced stochastic resonance phenomena under vibrational strong coupling, which have been suggested as a plausible theoretical mechanism to explain the experimentally observed resonance phenomena in the absence of periodic driving that has not yet been fully understood.