Polyatomic Thermal Radiative Dissociation in Microcavities

Abstract

Blackbody infrared radiative dissociation (BIRD) activates molecules through successive absorption of ambient thermal photons until the internal energy reaches a dissociation threshold. Because these radiative transition rates depend on the electromagnetic density of states (DOS), structured infrared environments provide a route to control thermal unimolecular dissociation. Here we develop a state-resolved master-equation framework for polyatomic BIRD in a planar Au/MgO multilayer cavity, where the reactive cluster $\mathrm{(H_2O)_2Cl^-}$ is studied. The cavity modifies the kinetics through the DOS sampled by anharmonic fundamental, overtone, and combination transitions. We show that MgO surface phonon polaritons produce strong near-field enhancements in the central vacuum reaction region of a microcavity. We find that short cavities with thick polar crystal layers yield the largest BIRD enhancements due to enhanced evanescent surface phonon polariton contributions. We further include collisions with a methane bath gas and show that cavity DOS engineering shifts the crossover between BIRD and collisional activation. These results establish Reststrahlen-band DOS engineering as a practical strategy for controlling polyatomic BIRD in infrared microcavities.