Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104.
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104;
Proc Natl Acad Sci U S A. 2020 Aug 4;117(31):18324-18331. doi: 10.1073/pnas.2009272117. Epub 2020 Jul 17.
We simulate vibrational strong coupling (VSC) and vibrational ultrastrong coupling (V-USC) for liquid water with classical molecular dynamics simulations. When the cavity modes are resonantly coupled to the O-H stretch mode of liquid water, the infrared spectrum shows asymmetric Rabi splitting. The lower polariton (LP) may be suppressed or enhanced relative to the upper polariton (UP) depending on the frequency of the cavity mode. Moreover, although the static properties and the translational diffusion of water are not changed under VSC or V-USC, we do find the modification of the orientational autocorrelation function of HO molecules especially under V-USC, which could play a role in ground-state chemistry.
我们使用经典分子动力学模拟模拟了液体水的振动强耦合（VSC）和振动超耦合（V-USC）。当腔模与液体水的 O-H 伸缩模式共振耦合时，红外光谱显示出不对称的拉比分裂。下极化激元（LP）相对于上极化激元（UP）可能被抑制或增强，具体取决于腔模的频率。此外，尽管 VSC 或 V-USC 下液体水的静态性质和平移扩散没有改变，但我们确实发现 HO 分子的取向自相关函数的变化，特别是在 V-USC 下，这可能在基态化学中起作用。
