Entropy of Simulated Liquids Using Multiscale Cell Correlation.
Entropy of Simulated Liquids Using Multiscale Cell Correlation.
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DOI：
10.3390/e21080750
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发表时间：
2019-07-31
期刊：
影响因子：
--
通讯作者：
Henchman RH
中科院分区：
文献类型：
--
作者：
Ali HS;Higham J;Henchman RH
精确计算液体的熵是一个重要的目标，因为许多过程都发生在液相中。几乎同样重要的是理解所获得的值。然而，很少有方法可以计算这样的系统的熵，更少的是使获得的值有意义。我们提出了我们的多尺度细胞相关（MCC）的方法来计算熵的液体分子动力学模拟。该方法使用力和扭矩在分子和联合原子水平和分子的配位和构象的概率分布。与以前的工作的主要区别是一致的治疗的平均场细胞近似的approriate自由度，分离的力和扭矩协方差矩阵，并列入多个二面角分子的构象相关性。MCC适用于更广泛的一组56种重要的工业液体建模使用广义琥珀力场（GAFF）和优化的潜力液体模拟（OPLS）力场与1.14*CM1A电荷。GAFF和OPLS的无符号误差与实验熵分别为8.7 J K mol和9.8 J K mol。这是显着优于2相热力学方法的分子的子集在共同的，这是唯一的其他方法，已被应用到这样的系统。MCC通过提供分子和联合原子水平上的平移和旋转振动熵以及拓扑熵的分解，清楚地说明了为什么熵具有它所具有的价值。
Accurately calculating the entropy of liquids is an important goal, given that many processes take place in the liquid phase. Of almost equal importance is understanding the values obtained. However, there are few methods that can calculate the entropy of such systems, and fewer still to make sense of the values obtained. We present our multiscale cell correlation (MCC) method to calculate the entropy of liquids from molecular dynamics simulations. The method uses forces and torques at the molecule and united-atom levels and probability distributions of molecular coordinations and conformations. The main differences with previous work are the consistent treatment of the mean-field cell approximation to the approriate degrees of freedom, the separation of the force and torque covariance matrices, and the inclusion of conformation correlation for molecules with multiple dihedrals. MCC is applied to a broader set of 56 important industrial liquids modeled using the Generalized AMBER Force Field (GAFF) and Optimized Potentials for Liquid Simulations (OPLS) force fields with 1.14*CM1A charges. Unsigned errors versus experimental entropies are 8.7 J K mol for GAFF and 9.8 J K mol for OPLS. This is significantly better than the 2-Phase Thermodynamics method for the subset of molecules in common, which is the only other method that has been applied to such systems. MCC makes clear why the entropy has the value it does by providing a decomposition in terms of translational and rotational vibrational entropy and topographical entropy at the molecular and united-atom levels.
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影响因子：
5.5
作者：
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