Cavity-Modified Chemiluminescent Reaction of Dioxetane

[Image: see text] Chemiluminescence is a thermally activated chemical process that emits a photon of light by forming a fraction of products in the electronic excited state. A well-known example of this spectacular phenomenon is the emission of light in the firefly beetle, where the formation of a four-membered cyclic peroxide compound and subsequent dissociation produce a light-emitting product. The smallest cyclic peroxide, dioxetane, also exhibits chemiluminescence but with a low quantum yield as compared to that of firefly dioxetane. Employing the strong light–matter coupling has recently been found to be an alternative strategy to modify the chemical reactivity. In the presence of an optical cavity, the molecular degrees of freedom greatly mix with the cavity mode to form hybrid cavity–matter states called polaritons. These newly generated hybrid light–matter states manipulate the potential energy surfaces and significantly change the reaction dynamics. Here, we theoretically investigate the effects of a strong light–matter interaction on the chemiluminescent reaction of dioxetane using the extended Jaynes–Cummings model. The cavity couplings corresponding to the electronic and vibrational degrees of freedom have been included in the interaction Hamiltonian. We explore how the cavity alters the ground- and excited-state path energy barriers and reaction rates. Our results demonstrate that the formation of excited-state products in the dioxetane decomposition process can be either accelerated or suppressed, depending on the molecular orientation with respect to the cavity polarization.