Vibrational strong coupling in liquid water from cavity molecular dynamics
Vibrational strong coupling in liquid water from cavity molecular dynamics
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DOI：
10.1063/5.0156808
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发表时间：
2023-06-21
影响因子：
4.4
通讯作者：
Manolopoulos, David E.
中科院分区：
文献类型：
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作者：
Lieberherr, Annina Z.;Furniss, Seth T. E.;Manolopoulos, David E.
我们评估了腔分子动力学方法的振动极化激元光谱的计算使用液体水作为一个具体的例子。我们开始争论最近的建议，核量子效应可能会导致扩大的极化激元带，而不是发现它们只是导致非谐波红移的极化激元频率。我们继续表明，我们的模拟腔光谱可以再现图形精度与谐波模型，仅使用腔的自由光谱和腔的几何形状作为输入。最后，我们表明，这个谐波模型可以与实验的无腔光谱，得到的结果与光学腔测量吻合得很好。由于输入到我们的谐波模型是等效的输入到应用光学的传输矩阵方法，我们得出结论，腔分子动力学不能提供任何更多的洞察力的影响，振动强耦合的吸收光谱比这种传输矩阵方法，这已经被实验学家广泛使用，以证实他们的腔结果。
We assess the cavity molecular dynamics method for the calculation of vibrational polariton spectra using liquid water as a specific example. We begin by disputing a recent suggestion that nuclear quantum effects may lead to a broadening of polariton bands, finding instead that they merely result in anharmonic red shifts in the polariton frequencies. We go on to show that our simulated cavity spectra can be reproduced to graphical accuracy with a harmonic model that uses just the cavity-free spectrum and the geometry of the cavity as input. We end by showing that this harmonic model can be combined with the experimental cavity-free spectrum to give results in good agreement with optical cavity measurements. Since the input to our harmonic model is equivalent to the input to the transfer matrix method of applied optics, we conclude that cavity molecular dynamics cannot provide any more insight into the effect of vibrational strong coupling on the absorption spectrum than this transfer matrix method, which is already widely used by experimentalists to corroborate their cavity results.