Molinero Valeria, Moore Emily B
Department of Chemistry, University of Utah, Salt Lake City, 84112, USA.
J Phys Chem B. 2009 Apr 2;113(13):4008-16. doi: 10.1021/jp805227c.
Water and silicon are chemically dissimilar substances with common physical properties. Their liquids display a temperature of maximum density, increased diffusivity on compression, and they form tetrahedral crystals and tetrahedral amorphous phases. The common feature to water, silicon, and carbon is the formation of tetrahedrally coordinated units. We exploit these similarities to develop a coarse-grained model of water (mW) that is essentially an atom with tetrahedrality intermediate between carbon and silicon. mW mimics the hydrogen-bonded structure of water through the introduction of a nonbond angular dependent term that encourages tetrahedral configurations. The model departs from the prevailing paradigm in water modeling: the use of long-ranged forces (electrostatics) to produce short-ranged (hydrogen-bonded) structure. mW has only short-range interactions yet it reproduces the energetics, density and structure of liquid water, and its anomalies and phase transitions with comparable or better accuracy than the most popular atomistic models of water, at less than 1% of the computational cost. We conclude that it is not the nature of the interactions but the connectivity of the molecules that determines the structural and thermodynamic behavior of water. The speedup in computing time provided by mW makes it particularly useful for the study of slow processes in deeply supercooled water, the mechanism of ice nucleation, wetting-drying transitions, and as a realistic water model for coarse-grained simulations of biomolecules and complex materials.
水和硅是化学性质不同但具有共同物理性质的物质。它们的液体表现出最大密度温度、压缩时扩散率增加,并且会形成四面体晶体和四面体非晶相。水、硅和碳的共同特征是形成四面体配位单元。我们利用这些相似性开发了一种水的粗粒度模型(mW),它本质上是一个四面体性介于碳和硅之间的原子。mW通过引入一个依赖于非键角的项来模拟水的氢键结构,该项有利于四面体构型。该模型背离了水建模中的主流范式:使用长程力(静电作用)来产生短程(氢键)结构。mW仅具有短程相互作用,但它能再现液态水的能量、密度和结构,以及其异常现象和相变,与最流行的水原子模型相比,具有相当或更高的精度,而计算成本不到1%。我们得出结论,决定水的结构和热力学行为的不是相互作用的性质,而是分子的连接性。mW在计算时间上的加速使得它对于研究深度过冷水的缓慢过程、冰核形成机制、干湿转变以及作为生物分子和复杂材料粗粒度模拟的现实水模型特别有用。