Catalysis by Dark States in Vibropolaritonic Chemistry
Catalysis by Dark States in Vibropolaritonic Chemistry
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DOI：
10.1103/physrevlett.128.096001
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发表时间：
2022-02-28
影响因子：
8.6
通讯作者：
Yuen-Zhou, Joel
中科院分区：
文献类型：
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作者：
Du, Matthew;Yuen-Zhou, Joel
N个局域分子振动的无序系综与一个共振光学腔模之间的集体强耦合产生了两个极化子和N-1>；>；2暗模式。因此，由于极化子的形成而引起的热激活反应动力学的实验变化似乎是不太可能的，仍然是一个谜。在这里，我们展示了被忽视的暗模式，虽然停留在与裸分子振动相同的能量处，但在类似于2-3个分子的地方被强劲地离域，产生增强的振动冷却通道，同时催化化学反应。作为说明，我们从理论上证明，由于增强了产品的稳定性，电子转移速率大约增加了50%。当暗模式的均匀线宽小于它们的能量间隔时，可能会出现所报道的效应。
Collective strong coupling between a disordered ensemble of N localized molecular vibrations and a resonant optical cavity mode gives rise to two polariton and N - 1 >> 2 dark modes. Thus, experimental changes in thermally activated reaction kinetics due to polariton formation appear entropically unlikely and remain a puzzle. Here we show that the overlooked dark modes, while parked at the same energy as bare molecular vibrations, are robustly delocalized across similar to 2-3 molecules, yielding enhanced channels of vibrational cooling, concomitantly catalyzing a chemical reaction. As an illustration, we theoretically show an approximate to 50% increase in an electron transfer rate due to enhanced product stabilization. The reported effects can arise when the homogeneous linewidths of the dark modes are smaller than their energy spacings.