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

Frequency-Dependent Sternheimer Linear-Response Formalism for Strongly Coupled Light–Matter Systems

The rapid progress in quantum-optical experiments, especially in the field of cavity quantum electrodynamics and nanoplasmonics, allows one to substantially modify and control chemical and physical properties of atoms, molecules, and solids by strongly coupling to the quantized field. Alongside such experimental advances has been the recent development of ab initio approaches such as quantum electrodynamical density-functional theory (QEDFT), which is capable of describing these strongly coupled systems from first principles. To investigate response properties of relatively large systems coupled to a wide range of photon modes, ab initio methods that scale well with system size become relevant. In light of this, we extend the linear-response Sternheimer approach within the framework of QEDFT to efficiently compute excited-state properties of strongly coupled light–matter systems. Using this method, we capture features of strong light–matter coupling both in the dispersion and absorption properties of a molecular system strongly coupled to the modes of a cavity. We exemplify the efficiency of the Sternheimer approach by coupling the matter system to the continuum of an electromagnetic field. We observe changes in the spectral features of the coupled system as Lorentzian line shapes turn into Fano resonances when the molecule interacts strongly with the continuum of modes. This work provides an alternative approach for computing efficiently excited-state properties of large molecular systems interacting with the quantized electromagnetic field

Cavity Born–Oppenheimer Hartree–Fock Ansatz: Light–Matter Properties of Strongly Coupled Molecular Ensembles

Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, the current understanding of the interplay between molecules and confined light modes is incomplete. Accurate theoretical models that take into account intermolecular interactions to describe ensembles are therefore essential to understand the mechanisms governing polaritonic chemistry. We present an ab initio Hartree–Fock ansatz in the framework of the cavity Born–Oppenheimer approximation and study molecules strongly interacting with an optical cavity. This ansatz provides a nonperturbative, self-consistent description of strongly coupled molecular ensembles, taking into account the cavity-mediated dipole self-energy contributions. To demonstrate the capability of the cavity Born–Oppenheimer Hartree–Fock ansatz, we study the collective effects in ensembles of strongly coupled diatomic hydrogen fluoride molecules. Our results highlight the importance of the cavity-mediated intermolecular dipole–dipole interactions, which lead to energetic changes of individual molecules in the coupled ensemble