用分子密度泛函理论快速计算溶剂化自由能：热力学-包封偏摩尔体积修正
Fast Computation of Solvation Free Energies with Molecular Density Functional Theory: Thermodynamic-Ensemble Partial Molar Volume Corrections
摘要：
分子密度泛函理论（MDFT）提供了一种有效的隐式溶剂方法来估计分子的溶剂化自由能，同时保持了溶剂的完全分子表示。即使在一个二阶近似的自由能功能，所谓的均匀参考UID近似，我们表明，水合自由能计算的数据集的500种有机化合物的质量相似的那些从分子动力学自由能微扰模拟，与计算机成本降低了两到三个数量级。这就需要引入适当的部分体积校正，将结果从大正则系综转换为与实验相关的等压等温系综。我们表明，这种校正可以扩展到3D-RISM计算，给出了一个健全的理论justifcation最近提出的经验偏摩尔体积校正。
英文摘要：
Molecular Density Functional Theory (MDFT) offers an efficient implicit- solvent method to estimate molecule solvation free-energies whereas conserving a fully molecular representation of the solvent. Even within a second order ap- proximation for the free-energy functional, the so-called homogeneous reference uid approximation, we show that the hydration free-energies computed for a dataset of 500 organic compounds are of similar quality as those obtained from molecular dynamics free-energy perturbation simulations, with a computer cost reduced by two to three orders of magnitude. This requires to introduce the proper partial volume correction to transform the results from the grand canoni- cal to the isobaric-isotherm ensemble that is pertinent to experiments. We show that this correction can be extended to 3D-RISM calculations, giving a sound theoretical justifcation to empirical partial molar volume corrections that have been proposed recently.
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