Cavity-Modified Unimolecular Dissociation Reactions viaIntramolecular Vibrational Energy Redistribution

While the emergingfield of vibrational polariton chemistry has thepotential to overcome traditional limitations of synthetic chemistry, theunderlying mechanism is not yet well understood. Here, we explore how thedynamics of unimolecular dissociation reactions that are rate-limited byintramolecular vibrational energy redistribution (IVR) can be modified insidean infrared optical cavity. We study a classical model of a bent triatomic molecule,where the two outer atoms are bound by anharmonic Morse potentials to thecenter atom coupled to a harmonic bending mode. We show that an optical cavityresonantly coupled to particular anharmonic vibrational modes can interfere withIVR and alter unimolecular dissociation reaction rates when the cavity mode actsas a reservoir for vibrational energy. These results lay the foundation for furthertheoretical work toward understanding the intriguing experimental results ofvibrational polaritonic chemistry within the context of IVR

Automated summary

This study explores the influence of an optical cavity on intramolecular vibrational energy redistribution and demonstrates that optical cavity resonance coupling can alter the rates of unimolecular dissociation reactions.