Centre for Molecular Simulation, Swinburne University of Technology, P.O. Box 218, Hawthorn, Victoria 3122, Australia.
J Chem Phys. 2017 Jun 28;146(24):244504. doi: 10.1063/1.4986917.
The ability of ab initio interatomic potentials to accurately predict vapor-liquid phase equilibria is investigated. Monte Carlo simulations are reported for the vapor-liquid equilibria of argon and krypton using recently developed accurate ab initio interatomic potentials. Seventeen interatomic potentials are studied, formulated from different combinations of two-body plus three-body terms. The simulation results are compared to either experimental or reference data for conditions ranging from the triple point to the critical point. It is demonstrated that the use of ab initio potentials enables systematic improvements to the accuracy of predictions via the addition of theoretically based terms. The contribution of three-body interactions is accounted for using the Axilrod-Teller-Muto plus other multipole contributions and the effective Marcelli-Wang-Sadus potentials. The results indicate that the predictive ability of recent interatomic potentials, obtained from quantum chemical calculations, is comparable to that of accurate empirical models. It is demonstrated that the Marcelli-Wang-Sadus potential can be used in combination with accurate two-body ab initio models for the computationally inexpensive and accurate estimation of vapor-liquid phase equilibria.
研究了从头算原子间势准确预测汽液平衡的能力。使用最近开发的准确从头算原子间势，报道了氩气和氪气汽液平衡的蒙特卡罗模拟。研究了十七种原子间势，它们是由两种体加三种体项的不同组合构成的。模拟结果与从三相点到临界点的各种条件下的实验或参考数据进行了比较。结果表明，通过添加基于理论的项，从头算势的使用可以系统地提高预测的准确性。使用 Axilrod-Teller-Muto 和其他多极贡献以及有效 Marcelli-Wang-Sadus 势来考虑三体相互作用的贡献。结果表明，从量子化学计算中获得的最新原子间势的预测能力与准确的经验模型相当。结果表明，Marcelli-Wang-Sadus 势可以与准确的两体从头算模型结合使用，以便在计算上经济高效且准确地估算汽液平衡。
