Polaritonic control of blackbody infrared radiative dissociation

Vibrational strong light-matter coupling offers a promising approach for controlling chemical reactivity with infrared microcavities. While recent research has examined potential mechanisms for this phenomenon, many important questions remain, including what type of reactions can be modified and to what extent this modification can be achieved. In this study, we explore the dynamics of Blackbody Infrared Radiative Dissociation (BIRD) in microcavities under weak and strong light-matter interaction regimes. In the BIRD process, molecules absorb infrared photons from blackbody radiation, gradually accumulating energy until dissociation occurs. Hence, these reaction rates depend heavily on the thermal radiation spectrum, which is expected to be significantly different inside an optical microcavity. Using a Master equation approach, we developed a kinetic model for the population of bound vibrational states commanded by the absorption and emission of photons. This approach allowed us to employ a detailed description of the photonic environment across all relevant frequencies and consider all possible transitions including anharmonic effects. We present a framework explaining how infrared microcavities influence BIRD kinetics, emphasizing the importance of, often neglected, overtone transitions. Our findings [1] outline the conditions under which significant enhancement or mild suppression of BIRD rates can be achieved, offering insights into the practical limitations and new strategies for controlling chemistry within infrared resonators.

[1] Suyabatmaz, E., Aroeira, G. J. R., Ribeiro, R. F., “Polaritonic control of blackbody infrared radiative dissociation“, 2024, arXiv:2409.09000 [physics.chem-ph]