论文标题

在光泽和阴影之间挥杆:热激活颤动的化学的理论进步(一个透视)

Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)

论文作者

Campos-Gonzalez-Angulo, Jorge A., Poh, Yong Rui, Du, Matthew, Yuen-Zhou, Joel

论文摘要

Polariton化学已成为合成化学的吸引人分支,该分支有望选择模式选择性和一种更清洁的动力学控制方法。特别令人感兴趣的是众多实验,在没有光泵的情况下,通过在红外光学微腔内进行反应来改变反应性。这项工作被称为“颤音性化学”。这些观察结果的最佳条件是(1)正常入射率($ k = 0 $)之间的腔与反应模式之间的共振,以及(2)效果的单调增加,样品中发射器的浓度。重要的是,仅在所谓的“集体”强耦合方案中实验证明了颤动的化学,其中有一个宏观数量的分子(而不是单个分子)与微腔的每个光子模式耦合。令人惊讶的是,从概念的角度来理解这一现象的努力已经遇到了几个障碍,迄今为止,没有一个单一的统一理论浮出水面。该观点记录了理论家采取的最相关的方法,从每项工作中提出了贡献和尚未解决的挑战。我们预计该手稿不仅可以成为实验者和理论家的入门,而且还为未来的努力提供了努力,以寻求颤音性化学动力学的最终形式主义。

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) 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 manuscript 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.

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