Institute of Physical Chemistry and Center for Computational Sciences, Johannes Gutenberg University of Mainz , Staudinger Weg 7, 55128 Mainz, Germany.
J Am Chem Soc. 2014 Mar 5;136(9):3395-9. doi: 10.1021/ja411161a. Epub 2014 Feb 19.
The interpretation of the X-ray spectra of water as evidence for its asymmetric structure has challenged the traditional nearly tetrahedral model and initiated an intense debate about the order and symmetry of the hydrogen-bond network in water. Here, we present new insights into the nature of local interactions in ice and liquid water obtained using a first-principle energy decomposition method. A comparative analysis shows that the majority of molecules in liquid water in our simulation exhibit hydrogen-bonding energy patterns similar to those in ice and retain the four-fold coordination with only moderately distorted tetrahedral configurations. Although this result indicates that the traditional description of liquid water is fundamentally correct, our study also demonstrates that for a significant fraction of molecules the hydrogen-bonding environments are highly asymmetric with extremely weak and distorted bonds.
水的 X 射线光谱的解释作为其非对称结构的证据，挑战了传统的近乎四面体模型，并引发了关于水的氢键网络的有序性和对称性的激烈争论。在这里，我们使用第一性原理能量分解方法，对冰和液态水中局部相互作用的性质提出了新的认识。比较分析表明，在我们的模拟中，液态水中的大多数分子表现出与冰相似的氢键能模式，并保持四配位，只有略微扭曲的四面体构型。尽管这一结果表明传统的液态水描述在根本上是正确的，但我们的研究也表明，对于相当一部分分子，氢键环境具有高度的不对称性，键非常弱且扭曲。
