Control of Blackbody Infrared Radiative Dissociation in Microcavities

Recent experimental observations indicate that vibrational strong light-matter coupling can modify chemical reactivity within infrared microcavities; however, the theoretical understanding remains limited. In this work, we propose a new approach to cavity control of reactivity by investigating Blackbody Infrared Radiative Dissociation (BIRD) through vibrational strong coupling in infrared microcavities under diverse conditions. BIRD, a process driven by the absorption of background thermal radiation that induces molecular vibrations leading to bond dissociation, experiences significantly altered rates in confined electromagnetic environments.

Using a theoretical framework based on coupled reaction kinetics, we calculate BIRD rates by solving coupled differential equations that account for absorption and emission rates between vibrational levels, adapting these rates for weak and strong coupling scenarios in selected molecular systems. Our results demonstrate how microcavity parameters, including cavity length, light-matter interaction strength, and the selection of specific strongly coupled material systems, modify the thermal radiation-induced dissociation of diatomics compared to free space. We highlight optimal conditions for either enhancing or suppressing BIRD in weak and strong coupling regimes. Our findings offer new insights into the impact of strong light-matter interactions on the BIRD process, providing strategies to control this phenomenon within microcavities.