论文标题
核量子对水气接口的振动动力学影响
Nuclear quantum effects on the vibrational dynamics of the water-air interface
论文作者
论文摘要
我们已经应用了路径积分分子动力学模拟，以研究对水空气界面上水分子振动动力学的核量子效应。使用小波的时间序列分析方法计算了O-H伸展模式频率中的瞬时波动，而振动光谱扩散的时间尺度是由频率时间相关函数和关节概率分布以及氢键相关功能确定的。我们发现，核量子效应的纳入不仅会导致振动频率分布的红移约为120 〜cm $^{ - 1} $，用于散装和界面水分子，还导致了水空气界面上振动动力学的加速。此外，与散装相比，在界面水分子的振动频率分布中可以看到约30〜cm $^{ - 1} $的蓝光。此外，发现水分子的动力学超出了两个分子层，与大量水基本上相似。
We have applied path integral molecular dynamics simulations to investigate nuclear quantum effects on the vibrational dynamics of water molecules at the water-air interface. The instantaneous fluctuations in the frequencies of the O-H stretch modes are calculated using the wavelet method of time series analysis, while the time scales of vibrational spectral diffusion are determined from frequency-time correlation functions and joint probability distributions, as well as the hydrogen bond number correlation functions. We find that the inclusion of nuclear quantum effects leads not only to a redshift in the vibrational frequency distribution by about 120~cm$^{-1}$ for both the bulk and interfacial water molecules, but also to an acceleration of the vibrational dynamics on the water-air interface by as much as 60$\%$. In addition, a blueshift of about 30 ~cm$^{-1}$ is seen in the vibrational frequency distribution of interfacial water molecules compared to that of the bulk. Furthermore, the dynamics of water molecules beyond the topmost two molecular layers was found to be essentially similar to that of bulk water.
