Swinging between shine and shadow: Theoretical advances on thermally activated vibropolaritonic chemistry
Swinging between shine and shadow: Theoretical advances on thermally activated vibropolaritonic chemistry
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DOI：
10.1063/5.0143253
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发表时间：
2023-06-21
影响因子：
4.4
通讯作者：
Yuen-Zhou, J.
中科院分区：
文献类型：
--
作者：
Campos-Gonzalez-Angulo, J. A.;Poh, Y. R.;Yuen-Zhou, J.
极化化学已经成为合成化学的一个吸引人的分支，它承诺模式选择性和更清洁的动力学控制方法。特别令人感兴趣的是，在没有光泵浦的情况下，通过在红外光学微腔内进行反应来改变反应性的许多实验；这种努力被称为“振动极化化学”。这些观测的最佳条件是(1)在正常入射（k = 0）下腔模式和反应模式之间的共振(2)随样品中发射体浓度的增加而单调增加。重要的是，振动极化化学仅在所谓的“集体”强耦合状态下得到实验证明，在这种状态下，微腔的每个光子模式都有宏观数量的分子（而不是单个分子）耦合。引人注目的是，从概念角度理解这一现象的努力遇到了几个障碍，到目前为止还没有一个统一的理论浮出水面。本展望记录了理论家所采取的最相关的方法，列出了每项工作的贡献和未解决的挑战。我们期望这一观点不仅可以作为实验学家和理论家的入门读物，而且还可以为未来寻求振动极化化学动力学的最终形式提供信息。
Polariton chemistry has emerged as an appealing branch of synthetic chemistry that promises mode selectivity and a cleaner approach to kinetic control. Of particular interest are the numerous experiments in which reactivity has been modified by virtue of performing the reaction inside infrared optical microcavities in the absence of optical pumping; this effort is known as "vibropolaritonic chemistry." The optimal conditions for these observations are (1) resonance between cavity and reactive modes at normal incidence (k = 0) and (2) a monotonic increase of the effect with the concentration of emitters in the sample. Importantly, vibropolaritonic chemistry has only been experimentally demonstrated in the so-called "collective" strong coupling regime, where there is a macroscopic number of molecules (rather than a single molecule) coupled to each photon mode of the microcavity. Strikingly, efforts to understand this phenomenon from a conceptual standpoint have encountered several roadblocks, and no single, unifying theory has surfaced thus far. This Perspective documents the most relevant approaches taken by theorists, laying out the contributions and unresolved challenges from each work. We expect this Perspective to not only serve as a primer for experimentalists and theorists alike but also inform future endeavors in the quest for the ultimate formalism of vibropolaritonic chemical kinetics.