振动极化激元化学中的暗态催化作用
Catalysis by Dark States in Vibropolaritonic Chemistry
摘要：
$N$局域分子振动的无序系综与共振光腔模之间的集体强耦合产生2极化激元和$N-1\gg2$暗模。因此，由于极化激元的形成，热激活反应动力学的实验变化似乎熵不太可能，仍然是一个谜。在这里，我们表明，被忽视的暗模式，而停放在相同的能量作为裸分子振动，是强大的离域跨越$\sim$ 2-3分子，产生振动冷却的增强通道，伴随着催化化学反应。作为一个例子，我们理论上表明，由于增强的产品稳定性，电子转移速率增加了$\approx$ 50\%。当暗模的均匀线宽小于它们的能量间距时，会出现所报道的效应。
英文摘要：
Collective strong coupling between a disordered ensemble of $N$ localized molecular vibrations and a resonant optical cavity mode gives rise to 2 polariton and $N-1\gg2$ 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 $\sim$2-3 molecules, yielding enhanced channels of vibrational cooling, concomitantly catalyzing a chemical reaction. As an illustration, we theoretically show a $\approx$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.
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