美国加州大学Sheldon Matthew团队报道了，振动弱耦合和强耦合通过腔体介导的辐射能量传递改变化学反应。相关研究成果于2025年1月16日发表在《自然—化学》。

通过外部影响控制反应结果是化学的核心目标。与传统的热化学和光化学方法相比，分子振动和腔模之间的振动耦合正迅速成为一种独特的策略；然而，对基本机制的了解仍然有限。

该文中，研究人员研究了等离子体纳米腔中的振动弱耦合和强耦合，如何改变五水合硫酸铜的热脱水。研究证明，光-物质耦合将脱水的起始温度降低了14°C，研究人员将这种效应归因于共振电磁模式介导的增强辐射能量传输，消除了耦合系统中的温度梯度。

研究发现提供了直接证据，证明局部能量转移导致高光密度态特定区域的化学行为发生改变。

该项工作建立了一种使用光学腔修改热驱动化学过程的机制，对开发利用这些量身定制的相互作用，来实现目标反应控制的催化系统具有重要意义。

附：英文原文

Title: Vibrational weak and strong coupling modify a chemical reaction via cavity-mediated radiative energy transfer

Author: Brawley, Zachary T., Pannir-Sivajothi, Sindhana, Yim, Ju Eun, Poh, Yong Rui, Yuen-Zhou, Joel, Sheldon, Matthew

Issue&Volume: 2025-01-16

Abstract: Controlling reaction outcomes through external influences is a central goal in chemistry. Vibrational coupling between molecular vibrations and cavity modes is rapidly emerging as a distinct strategy compared with conventional thermochemical and photochemical methods; however, insight into the fundamental mechanisms remains limited. Here we investigate how vibrational weak and strong coupling in plasmonic nanocavities modifies the thermal dehydration of copper sulfate pentahydrate. We demonstrate that light–matter coupling reduces the onset temperature for dehydration by up to 14°C, and we attribute this effect to enhanced radiative energy transport that is mediated by resonant electromagnetic modes, eliminating temperature gradients in the coupled system. Our findings provide direct evidence of localized energy transfer leading to modified chemical behaviour in specific regions of high optical density of states. This work establishes a mechanism for modifying thermally driven chemical processes using optical cavities, with implications for the development of catalytic systems that exploit these tailored interactions to achieve targeted reaction control.

DOI: 10.1038/s41557-024-01723-6

Source: https://www.nature.com/articles/s41557-024-01723-6