Open Access
Cavity-Modified Unimolecular Dissociation Reactions via Intramolecular Vibrational Energy Redistribution
Author(s) -
Derek S. Wang,
Tomáš Neuman,
Susanne F. Yelin,
Johannes Flick
Publication year - 2022
Publication title -
the journal of physical chemistry letters
Language(s) - Uncategorized
Resource type - Journals
SCImago Journal Rank - 2.563
H-Index - 203
ISSN - 1948-7185
DOI - 10.1021/acs.jpclett.2c00558
Subject(s) - anharmonicity , intramolecular force , dissociation (chemistry) , chemistry , chemical physics , potential energy , atomic physics , molecular vibration , triatomic molecule , hot band , infrared , normal mode , redistribution (election) , reaction dynamics , molecular physics , molecule , vibration , physics , quantum mechanics , stereochemistry , organic chemistry , politics , political science , law
While the emerging field of vibrational polariton chemistry has the potential to overcome traditional limitations of synthetic chemistry, the underlying mechanism is not yet well understood. Here, we explore how the dynamics of unimolecular dissociation reactions that are rate-limited by intramolecular vibrational energy redistribution (IVR) can be modified inside an 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 the center atom coupled to a harmonic bending mode. We show that an optical cavity resonantly coupled to particular anharmonic vibrational modes can interfere with IVR and alter unimolecular dissociation reaction rates when the cavity mode acts as a reservoir for vibrational energy. These results lay the foundation for further theoretical work toward understanding the intriguing experimental results of vibrational polaritonic chemistry within the context of IVR.