Abstract
Strong light–matter coupling can modify the photochemistry of molecular systems. The collective dynamics of an ensemble of molecules coupled to the light field plays a crucial role in experimental observations. However, the theory of polaritonic chemistry is primarily understood in terms of single molecules, since even in small molecular ensembles the collective dynamics becomes difficult to disentangle. Understanding of the underlying ensemble mechanisms is key to a conceptual understanding and interpretation of experiments. We present a model system that simplifies the problem by mixing two-level Mg atoms with a single MgH+ molecule and investigate its collective dynamics. Our focus is on the modified chemical properties of a single diatomic molecule in the presence of an ensemble of resonant atoms as well as the structure of the major and intermediate polariton states. We present quantum dynamics simulations of the coupled vibronic–photonic system for a variable size of the atomic ensemble. Special attention is given to dissociative the dynamics of the MgH+ molecule.
Highlights
Strong coupling of molecules with quantized photon fields in optical cavities can be observed when the Rabi frequency exceeds the spontaneous decay rate
Strong coupling in nanocavities has been demonstrated to modify the reactivity of photochemical processes and to induce collective Rabi splittings on the order of hundreds of meV.[12−14] Here, the confined light field forms a hybrid state with molecular degrees of freedom
We have shown that the reactivity of an MgH+ molecule is modified by collective strong coupling with Mg atoms
Summary
Strong coupling of molecules with quantized photon fields in optical cavities can be observed when the Rabi frequency exceeds the spontaneous decay rate. A wide range of different experiments makes use of strong coupling in nanocavities.[1] A few examples of strong coupling with molecules include[2,3] spectroscopy on the polariton states,[4] modifications of intersystem crossing,[5] strong coupling in J-aggregates,[6,7] coherent control with quantum light,[8] vibrational strong coupling,[9,10] and strong coupling in plasmonic nanoparticles.[11] Strong coupling in nanocavities has been demonstrated to modify the reactivity of photochemical processes and to induce collective Rabi splittings on the order of hundreds of meV.[12−14] Here, the confined light field forms a hybrid state with molecular degrees of freedom. The molecular Jaynes−Cummings (JC) model has shown that strong light− matter coupling results in nonadiabatic dynamics,[16−18] analogous to avoided crossings and conical intersections.[19−22]
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