Enthalpies of mixing predicted using molecular dynamics simulations and OPLS force field
Enthalpies of mixing predicted using molecular dynamics simulations and OPLS force field
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DOI：
10.1016/j.fluid.2009.11.028
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发表时间：
2010-03-15
影响因子：
2.6
通讯作者：
Sun, Huai
中科院分区：
文献类型：
--
作者：
Dai, Jianxing;Li, Xiaofeng;Sun, Huai
混合焓（EOM）是混合物最基本的热力学性质之一。为了评估使用力场模拟方法预测EOM的可行性，使用基于ops和TINP力场的MD模拟研究了15（15）个具有代表性的二元混合物。对仿真条件和误差进行了仔细的检查。计算得到的EOM数据精度达到0.04 kJ/mol。然而，通过与实验数据的偏差来衡量的预测，只是在质量上正确。在影响预测精度的诸多因素中，代表不同分子间相互作用的力场质量起着最重要的作用。以甲醇/苯和乙醇/苯为例，我们证明了极化原子之间的非加性相互作用项可以显著提高预测质量。此外，为了准确地表示极化效应，似乎需要电荷相关的LJ参数。(C) 2009 Elsevier B.V.版权所有
Enthalpy of mixing (EOM) is one of the most basic thermodynamic properties of mixtures. To assess feasibility of predicting EOM using force field simulation methods, fifteen (15) representative binary mixtures were investigated using MD simulations based on OPLS and TINP force fields. The simulation conditions and errors were carefully examined. The precision level of 0.04 kJ/mol was obtained for calculated EOM data. However, the predictions, measured by deviations from experimental data, were only qualitatively correct. Among various factors influencing the accuracy of predictions, force field quality representing interactions among different molecules plays the most significant role. Using methanol/benzene and ethanol/benzene as examples, we demonstrated that non-additive interaction terms between polarizable atoms can be used to significantly improve the quality of predictions. In addition, it appears that charge-dependent LJ parameters are required in order to represent the polarization effects accurately. (C) 2009 Elsevier B.V. All rights reserved.