2021/09/09 by Derek S. Wang, Wang, Derek S, Tomáš Neuman +5 · 4 citations
Physics and Astronomy · #Chaotic Dynamics (nlin.CD) #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Mechanical and Optical Resonators #Quantum Electrodynamics and Casimir Effect #Quantum Physics (quant-ph) #Spectroscopy and Quantum Chemical Studies #Strong Light-Matter Interactions
paper · pdf · doi:10.48550/arxiv.2109.06631
openalex publication_date 2021/09/09 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
While the emerging field of vibrational polariton chemistry has the potential\nto overcome traditional limitations of synthetic chemistry, the underlying\nmechanism is not yet well understood. Here, we explore how the dynamics of\nunimolecular dissociation reactions that are rate-limited by intramolecular\nvibrational energy redistribution (IVR) can be modified inside an infrared\noptical cavity. We study a classical model of a bent triatomic molecule, where\nthe two outer atoms are bound by anharmonic Morse potentials to the center atom\ncoupled to a harmonic bending mode. We show that an optical cavity resonantly\ncoupled to particular anharmonic vibrational modes can interfere with IVR and\nalter unimolecular dissociation reaction rates when the cavity mode acts as a\nreservoir for vibrational energy. We find a strong dependence on the initial\nstate of the cavity and molecule. In particular, when the cavity is initially\nempty, the dissociation rate decreases, while when the cavity is initially\nhotter than the molecule, the cavity can instead accelerate the reaction rate.\nThese results lay the foundation for further theoretical work toward\nunderstanding the intriguing experimental results of vibrational polaritonic\nchemistry within the context of IVR.\n