Speaker
Description
Molecular vibro-polaritons are currently discussed as a possible tool to modify ground-state reactivity. They arise when vibrational transitions couple strongly to an electromagnetic field, e.g in a cavity. We present numerical open-system quantum dynamics of thioacetylacetone (TAA) undergoing hydrogen transfer, coupled to a cavity mode and a bath. This model system, previously studied in [Fischer and Saalfrank Phys. Chem. Chem. Phys., 2023, 25, 1177], comprises an asymmetric potential energy surface (PES). By accounting for vibrational energy relaxation (VER), we provide reaction rates and corresponding photon-frequency dependent rate-profiles, exhibiting both, suppression and acceleration, depending on microscopic details.
To understand the numerical results, analytic expressions for the rate-profiles are provided by utilizing the Jaynes-Cummings model, while treating VER perturbatively. We attribute our findings to the formation of polariton states, representing the light-matter hybridization when the light mode is in resonance with a vibrational transition. Our results indicate that a full quantum treatment of both the cavity mode and the bath is required.