Resonant catalysis of thermally activated chemical reactions with vibrational polaritons
Resonant catalysis of thermally activated chemical reactions with vibrational polaritons
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DOI：
10.1038/s41467-019-12636-1
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发表时间：
2019-10-15
影响因子：
16.6
通讯作者：
Yuen-Zhou, Joel
中科院分区：
文献类型：
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作者：
Campos-Gonzalez-Angulo, Jorge A.;Ribeiro, Raphael F.;Yuen-Zhou, Joel
光和物质之间的相互作用产生新的量子态，其能量可以改变化学动力学。在系综振动强耦合（VSC）的制度，一个宏观数量N的分子跃迁耦合到每个谐振腔模式，产生两个混合轻物质（极化激元）模式和一个水库的N - 1暗态的化学动力学基本上是那些裸露的分子。这一事实似乎与最近报道的VSC下热激活基态电子态反应的修改相反。在这里，我们提供了一个VSC Marcus-Levich-Jortner电子转移模型，可能解决这个悖论：虽然熵有利于通过暗态通道的过境，化学动力学可以由几个极化激元通道较小的活化能。催化变结构效应在轻物质共振时最大，与实验观察一致。
Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number N of molecular transitions couple to each resonant cavity mode, yielding two hybrid light-matter (polariton) modes and a reservoir of N - 1 dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC. Here we provide a VSC Marcus-Levich-Jortner electron transfer model that potentially addresses this paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies. The effects of catalytic VSC are maximal at light-matter resonance, in agreement with experimental observations.