Modification of ground state chemical reactivity via light-matter coherence in infrared cavities

20 March 2023, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Reaction-rate modifications for chemical processes have been reported due to strong coupling between reactant molecular vibrations and the cavity vacuum, however, no accepted mechanisms explain these observations. In this work, reaction-rate constants are extracted from evolving cavity transmission spectra, revealing resonant suppression of the intracavity reaction rate for alcoholysis of phenyl isocyanate with cyclohexanol. We observe up to an 80% suppression of the rate by tuning cavity modes to be resonant with the reactant isocyanate (NCO) stretch, the product carbonyl (CO) stretch, and cooperative reactant-solvent modes (CH). These results are explained using an open quantum system model that predicts resonant modifications of chemical reactivity via light-matter quantum coherences that depopulate vibrational excited states, suggesting fundamental links between chemistry and quantum science to be explored.


strong coupling
quantum chemistry
vibrational strong coupling
cavity-modified chemistry


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.