Energy Landscapes and Reactivity: Light–Matter Polaritons and Gas-Phase Unimolecular Reactions

Chemists have long sought new ways to control chemical reactions. Vibrational polaritons formed through strong light–matter interaction offer a promising approach, motivating efforts toward mechanistic understanding and rational design. I will present our recent results on conformational switch and energy-transfer dynamics in a hydrogen-bonded phenol system under vibrational strong coupling, highlighting the detrimental role of energy disorder and a delocalization criterion for sustaining polaritonic effects. I will then shift to gas-phase reactions and discuss an unusual OH-roaming pathway in the unimolecular decay of atmospherically relevant carbonyl oxide intermediates, where non-thermal energy distribution influences the competition between product channels.