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Abstract Experiments have suggested that strong interactions between molecular ensembles and infrared microcavities can be employed to control chemical equilibria. Nevertheless, the primary mechanism and key features of the effect remain largely unexplored. In this work, we develop a theory of chemical equilibrium in optical microcavities, which allows us to relate the equilibrium composition of a mixture in different electromagnetic environments. Our theory shows that in planar microcavities under strong coupling with polyatomic molecules, hybrid modes formed between all dipole-active vibrations and cavity resonances contribute to polariton-assisted chemical equilibrium shifts. To illustrate key aspects of our formalism, we explore a model S_N2 reaction within a single-mode infrared resonator. Our findings reveal that chemical equilibria can be shifted towards either direction of a chemical reaction, depending on the oscillator strength and frequencies of reactant and product normal modes. Polariton-induced zero-point energy changes provide the dominant contributions, though the effects in idealized single-mode cavities tend to diminish quickly as the temperature and number of molecules increase. Our approach is valid in generic electromagnetic environments and paves the way for understanding and controlling chemical equilibria with microcavities. 

Abstract Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number$$N$$ $N$of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of$$N-1$$ $N-1$dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC. Here we provide a VSC Marcus–Levich–Jortner electron transfer model that potentially addresses this paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies. The effects of catalytic VSC are maximal at light–matter resonance, in agreement with experimental observations. 

Optical nonlinearities are key resources in the contemporary photonics toolbox, relevant to quantum gate operations and all-optical switches. Chemical modification is often used to control the nonlinear response of materials at the microscopic level, but on-the-fly manipulation of such response is challenging. Tunability of optical nonlinearities in the mid-infrared (IR) is even less developed, hindering its applications in chemical sensing or IR photonic circuitry. Here, we report control of vibrational polariton coherent nonlinearities by manipulation of macroscopic parameters such as cavity longitudinal length or molecular concentration. Further two-dimensional IR investigations reveal that nonlinear dephasing provides the dominant source of the observed ultrafast polariton nonlinearities. The reported phenomena originate from the nonlinear macroscopic polarization stemming from strong coupling between microscopic molecular excitations and a macroscopic photonic cavity mode. 

Selective vibrational energy transfer between molecules in the liquid phase, a difficult process hampered by weak intermolecular forces, is achieved through polaritons formed by strong coupling between cavity photon modes and donor and acceptor molecules. Using pump-probe and two-dimensional infrared spectroscopy, we found that the excitation of the upper polariton, which is composed mostly of donors, can efficiently relax to the acceptors within ~5 picoseconds. The energy-transfer efficiency can be further enhanced by increasing the cavity lifetime, suggesting that the energy transfer is a polaritonic process. This vibrational energy-transfer pathway opens doors for applications in remote chemistry, sensing mechanisms, and vibrational polariton condensation.