论文标题
使用CAR-PARRINELLO模拟和微观订单描述符,揭示两个本地偏爱的结构,这些结构具有不同的分子偶极矩和环境液体水中的动力学
Using Car-Parrinello simulations and microscopic order descriptors to reveal two locally favored structures with distinct molecular dipole moments and dynamics in ambient liquid water
论文作者
论文摘要
水对于生活和技术应用至关重要,主要是因为其独特的热力学和动态特性,通常是异常或违反直觉的。这些异常是由氢键波动引起的,这是对超冷水的研究证明的。但是,很难在环境条件下表征这些波动。在这里,我们填补了这一知识差距,这要归功于从头开始的分子动力学(MD)模拟技术。我们计算局部结构阶参数ζ,量化了配位壳的分离,并找到两个局部最受欢迎的结构或状态:高ζ和低ζ。平均而言,高ζ分子具有四面体排列,具有四个氢键,第一个和第二个配位壳很好地分开。低ζ分子的连接较少,部分合并了第一个和第二个壳。在径向分布函数中的同性含量点的出现以及在不同的长度尺度和时间标度下的集体密度波动表明,与超冷水的可用实验数据一致的两态模型在环境条件下也保持在环境条件下,正如我们通过分析两种水分子的振动频谱的确认。两种状态之间的结构差异的显着后果是,高ζ分子的偶极矩比低ζ高6%。同时,低ζ结构更加无序,角度波动更明显。这些差异也反映在环境条件下的动力学中。低ζ分子比高ζ更快地将它们的重新定向降低,并在0.2 ps内合并其协调壳,而高ζ将壳分离保留更长的时间。
Water is essential for life and technological applications, mainly for its unique thermodynamic and dynamic properties, often anomalous or counterintuitive. These anomalies result from the hydrogen-bonds fluctuations, as evidenced by studies for supercooled water. However, it is difficult to characterize these fluctuations under ambient conditions. Here, we fill this knowledge gap thanks to the Car-Parrinello ab initio molecular dynamics (MD) simulation technique. We calculate the local structural order parameter ζ, quantifying the coordination shells separation, and find two locally-favored structures or states: High-ζ and Low-ζ. On average, High-ζ molecules have a tetrahedral arrangement, with four hydrogen bonds, and the first and the second coordination shell well separated. The Low-ζ molecules are less connected, partially merging the first and the second shells. The appearance of isosbestic points in the radial distribution functions and the collective density fluctuations at different length scales and timescales reveal that the two-state model, consistent with available experimental data for supercooled water, also holds under ambient conditions, as we confirm by analyzing the vibrational spectrum of both types of water molecules. Significant consequences of the structural differences between the two states are that High-ζ molecules have a dipole moment 6 % higher than Low-ζ. At the same time, Low-ζ structures are more disordered and with more significant angular fluctuations. These differences are also reflected in the dynamics under ambient conditions. The Low-ζ molecules decorrelate their reorientation faster than High-ζ and merge their coordination shells within 0.2 ps, while the High-ζ preserve the shell separation for longer times.