Nuclear quantum effects and hydrogen bond fluctuations in water
Nuclear quantum effects and hydrogen bond fluctuations in water
复制标题
DOI：
10.1073/pnas.1308560110
复制
发表时间：
2013-09-24
影响因子：
11.1
通讯作者：
Manolopoulos, David E.
中科院分区：
文献类型：
--
作者：
Ceriotti, Michele;Cuny, Jerome;Manolopoulos, David E.
氢键（HB）对于我们理解水的性质至关重要。然而，尽管有大量的理论和实验研究，它仍然有一些惊喜。在这里，我们从从头算模拟，适当考虑核量子效应的分析表明，在液态水中的氢键质子的受体氧原子的方向上经历显着的偏移。这产生了一个小的，但不可忽略的一部分瞬态autoprotolysis事件，没有看到在模拟与经典的核。这些事件与电子密度的主要重排，所揭示的计算的Wannier中心和H-1化学位移的分析。我们还表明，量子涨落表现出显着的相关性，在相邻的HB，一致的质子短暂穿梭沿着水线。最后，我们提出了可能的影响，我们的理解如何扰动（溶剂化离子，界面和限制）可能会影响HB网络在水中。
The hydrogen bond (HB) is central to our understanding of the properties of water. However, despite intense theoretical and experimental study, it continues to hold some surprises. Here, we show from an analysis of ab initio simulations that take proper account of nuclear quantum effects that the hydrogen-bonded protons in liquid water experience significant excursions in the direction of the acceptor oxygen atoms. This generates a small but nonnegligible fraction of transient autoprotolysis events that are not seen in simulations with classical nuclei. These events are associated with major rearrangements of the electronic density, as revealed by an analysis of the computed Wannier centers and H-1 chemical shifts. We also show that the quantum fluctuations exhibit significant correlations across neighboring HBs, consistent with an ephemeral shuttling of protons along water wires. We end by suggesting possible implications for our understanding of how perturbations (solvated ions, interfaces, and confinement) might affect the HB network in water.