Reaction-rate modifications for chemical processes due to strong coupling between reactant molecular vibrations and the cavity vacuum have been reported; however, no currently accepted mechanisms explain these observations. In this work, reaction-rate constants were extracted from evolving cavity transmission spectra, revealing resonant suppression of the intracavity reaction rate for alcoholysis of phenyl isocyanate with cyclohexanol. We observed up to an 80% suppression of the rate by tuning cavity modes to be resonant with the reactant isocyanate (NCO) stretch, the product carbonyl (CO) stretch, and cooperative reactant-solvent modes (CH). These results were interpreted using an open quantum system model that predicted resonant modifications of the vibrational distribution of reactants from canonical statistics as a result of light–matter quantum coherences, suggesting links to explore between chemistry and quantum science.

Strong cavity coupling to molecular vibrations creates vibration-polaritons capable of modifying chemical reaction kinetics, product branching ratios, and charge transfer equilibria. However, the mechanisms impacting these molecular processes remain elusive. Furthermore, even basic elements determining the spectral properties of polaritons, such as selection rules, transition moments, and lifetimes are poorly understood. Here, we use two-dimensional infrared and filtered pump–probe spectroscopy to report clear spectroscopic signatures and relaxation dynamics of excited vibration-polaritons formed from the cavity-coupled NO band of nitroprusside. We apply an extended multi-level quantum Rabi model that predicts transition frequencies and strengths that agree well with our experiment. Notably, the polariton features decay ~3–4 times slower than the polariton dephasing time, indicating that they support incoherent population, a consequence of their partial matter character.

Vibrational strong coupling has emerged as a promising route for manipulating the reactivity of molecules inside infrared cavities. We develop a full-quantum methodology to study the unitary dynamics of a single anharmonic vibrational mode interacting with a quantized infrared cavity field. By comparing multi-configurational time-dependent Hartree simulations for an intracavity Morse oscillator with an equivalent formulation of the problem in Hilbert space, we describe for the first time the essential role of permanent dipole moments in the femtosecond dynamics of vibrational polariton wavepackets. We classify molecules into three general families according to the shape of their electric dipole function d_e(q) along the vibrational mode coordinate q. For polar species with a positive slope of the dipole function at equilibrium, an initial diabatic light–matter product state without vibrational or cavity excitations evolves into a polariton wavepacket with a large number of intracavity photons for interaction strengths at the conventional onset of ultrastrong coupling. This buildup of the cavity photon amplitude is accompanied by an effective lengthening of the vibrational mode that is comparable with a laser-induced vibrational excitation in free space. In contrast, polar molecules with a negative slope of the dipole function experience an effective mode shortening, under equivalent coupling conditions. We validate our predictions using realistic ab initio ground state potentials and dipole functions for HF and CO₂ molecules. We also propose a non-adiabatic state preparation scheme to generate vibrational polaritons with molecules near infrared nanoantennas for the spontaneous radiation of infrared quantum light.

We propose an experiment to find evidence of the formation of light-induced crossings provoked by cavity quantum radiation on simple molecules by using state-of-the-art optical cavities, molecular beams, pump-probe laser schemes, and velocity mapping detectors for fragmentation. The procedure is based on prompt excitation and subsequent dissociation in a three-state scheme of a polar diatomic molecule, with two ${}^1\mathrm{\Sigma }$ states (ground and first excited) coupled first by the UV pump laser and then by the cavity radiation, and a third fully dissociative state ${}^1\mathrm{\Pi }$ coupled through the delayed UV/V probe laser. The observed enhancement of photodissociation yields in the ${}^1\mathrm{\Pi }$ channel at given time delays between the pump and probe lasers unambiguously indicates the formation of a light-induced crossing between the two ${}^1\mathrm{\Sigma }$ field-dressed potential energy curves of the molecule. Also, the production of cavity photons out of the vacuum field state via nonadiabatic effects represents a showcase of a molecular dynamical Casimir effect. To simulate the experiment outcome, we perform ab initio coherent quantum dynamics of the molecule LiF subject to external lasers and quantum cavity interactions in the strong coupling regime, using a product grid representation of the total polaritonic wave function for both vibrational and photon degrees of freedom.

A sideband cooling strategy that incorporates (i) the dynamics induced by structured (non-Markovian) environments in the target and auxiliary systems and (ii) the optimally time-modulated interaction between them is developed. For the context of cavity optomechanics, when non-Markovian dynamics are considered in the target system, ground state cooling is reached at much faster rates and at a much lower phonon occupation number than previously reported. In contrast to similar current strategies, ground state cooling is reached here for coupling-strength rates that are experimentally accessible for the state-of-the-art implementations. After the ultrafast optimal-ground-state-cooling protocol is accomplished, an additional optimal control strategy is considered to maintain the phonon number as close as possible to the one obtained in the cooling procedure. Contrary to the conventional expectation, when non-Markovian dynamics are considered in the auxiliary system, the efficiency of the cooling protocol is undermined.