Modification of ground-state chemical reactivity via light–matter coherence in infrared cavities
Abstract
Reaction-rate modifications for chemical processes due to strong coupling between reactant molecular vibrations and the cavity vacuum have been reported; however, no currently accepted mechanisms explain these observations. In this work, reaction-rate constants were extracted from evolving cavity transmission spectra, revealing resonant suppression of the intracavity reaction rate for alcoholysis of phenyl isocyanate with cyclohexanol. We observed 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 were interpreted using an open quantum system model that predicted resonant modifications of the vibrational distribution of reactants from canonical statistics as a result of light–matter quantum coherences, suggesting links to explore between chemistry and quantum science.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Jun 16, 2023
- Source ID
- 10.1126/science.ade7147
Entities
People
- Blake S Simpkins
- Felipe Herrera
- Felipe Recabal
- Johan F Triana
- Wonmi Ahn
Organizations
- Bilkent University
- United States Naval Research Laboratory