Ab initio three-body interactions for water. II. Effects on structure and energetics of liquid
Ab initio three-body interactions for water. II. Effects on structure and energetics of liquid
复制标题
水的从头开始三体相互作用。
DOI：
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发表时间：
2003
期刊：
影响因子：
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通讯作者：
K. Szalewicz
中科院分区：
文献类型：
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作者：
E. Mas;R. Bukowski;K. Szalewicz
一种新的从头开始的三体势[E. M. Mas 等人，J. Chem。物理。 118, 4386 (2003)，先前的论文] 已与准确的从头算势 SAPT-5 一起用于环境条件下正则系综中液态水的蒙特卡罗模拟。对这些模拟的径向分布函数的分析说明了非加性力对液体氢键结构的深远影响。仅使用二体势的模拟给出的每个分子的氢键比实验观察到的要少，径向分布函数远离测量的函数，并且相对于实验值低估了内能。当引入三体效应时，所有这些量都变得非常接近实验量。特别是，我们表明三体效应会导致水分子重新定向，从而导致氢键数量显着增加。我们的模拟表明三体效应贡献 14.5...
A new ab initio three-body potential [E. M. Mas et al., J. Chem. Phys. 118, 4386 (2003), preceding paper] has been employed, together with an accurate ab initio pair potential SAPT-5s, in Monte Carlo simulations of liquid water in the canonical ensemble at ambient conditions. Analysis of radial distribution functions from these simulations illustrates the profound effect nonadditive forces have on the hydrogen-bonded structure of the liquid. Simulations using only the two-body potential give one hydrogen bond per molecule less than observed experimentally, radial distribution functions far from measured ones, and the internal energy underestimated relative to the experimental value. When three-body effects are introduced, all these quantities become significantly closer to experimental ones. In particular, we show that three-body effects result in a reorientation of water molecules leading to significantly increased number of hydrogen bonds. Our simulations indicate that three-body effects contribute 14.5...