美国海军研究实验室Blake S. Simpkins团队报道了红外腔中通过光-物质相干性改变基态化学反应性。相关研究成果于2023年6月16日发表在国际顶尖学术期刊《科学》。

由于反应物分子振动和空腔真空之间的强耦合，化学过程的反应速率发生了变化；然而，目前还没有公认的机制来解释这些观察结果。

该文中，从演化的腔透射光谱中提取了反应速率常数，揭示了环己醇对苯基异氰酸酯醇解的腔内反应速率的共振抑制。研究人员观察到，通过将腔模式调整为与反应物异氰酸酯（NCO）拉伸、产物羰基（CO）拉伸和协同反应物溶剂模式（CH）共振，可以抑制高达80%的速率。这些结果是使用开放量子系统模型解释的，该模型预测了由于光-物质量子相干性，从正则统计中反应物振动分布的共振变化，这表明化学和量子科学之间存在联系。

附：英文原文

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

Author: Wonmi Ahn, Johan F. Triana, Felipe Recabal, Felipe Herrera, Blake S. Simpkins

Issue&Volume: 2023-06-16

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.

DOI: ade7147

Source: https://www.science.org/doi/10.1126/science.ade7147