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

• 成果类型: Article
• 署名作者: Ahn, Wonmi; Triana, Johan F.; Recabal, Felipe; Herrera, Felipe; Simpkins, Blake S.
• 署名单位: Ihsan Dogramaci Bilkent University; Universidad de Santiago de Chile; United States Department of Defense; United States Navy; United States Naval Research Laboratory
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12308
• DOI: 10.1126/science.ade7147
• 发表日期: 2023-06-16
• 页码: 1165-1168
• 关键词: isocyanates; alcoholysis; microcavity; absorption; molecules; DYNAMICS; phase

摘要

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.