ISIS Department, STFC Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, Oxon, OX11 0QX, UK.
J Phys Chem B. 2011 Dec 8;115(48):14014-22. doi: 10.1021/jp2031219. Epub 2011 Jun 23.
The structure of water is the subject of a long and ongoing controversy. Unlike simpler liquids, where atomic interactions are dominated by strong repulsive forces at short distances and weaker attractive (van der Waals) forces at longer distances, giving rise to local atomic coordination numbers of order 12, water has pronounced and directional hydrogen bonds which cause the dense liquid close-packed structure to open out into a disordered and dynamic network, with coordination number 4-5. Here I show that water structure can be accurately represented as a mixture of two identical, interpenetrating, molecular species separated by common hydrogen bonds. Molecules of one type can form hydrogen bonds with molecules of the other type but cannot form hydrogen bonds with molecules of the same type. These hydrogen bonds are strong along the bond but weak with respect to changes in the angle between neighboring bonds. The observed pressure and temperature dependence of water structure and thermodynamic properties follow naturally from this choice of water model, and it also gives a simple explanation of the enduring claims based on spectroscopic evidence that water is a mixture of two components.
水的结构是一个长期存在且持续争论的主题。与简单液体不同,在简单液体中,原子间的相互作用在短距离上主要由强烈的排斥力主导,在较长距离上则由较弱的吸引力(范德华力)主导,导致局部原子配位数约为 12,而水具有明显的、有向的氢键,使密集的液态紧密堆积结构展开成无序和动态的网络,配位数为 4-5。在这里,我表明水的结构可以准确地表示为两种相同的、相互贯穿的分子物种的混合物,它们由共同的氢键分隔开。一种类型的分子可以与另一种类型的分子形成氢键,但不能与同类型的分子形成氢键。这些氢键在键上很强,但相对于相邻键之间角度的变化较弱。这种水模型选择自然地解释了水结构和热力学性质随压力和温度的变化,也为基于光谱证据的持久主张提供了简单的解释,即水是两种成分的混合物。