可极化分子流体自由能泛函的计算方法
A recipe for free-energy functionals of polarizable molecular fluids
摘要：
经典的密度泛函理论是研究非均匀液体平衡结构和自由能的最直接的方法，但需要为每种感兴趣的液体构建近似的自由能泛函。我们提出了一个一般的配方，用于构建功能的小分子液体的基础上，只有一个单一的溶剂分子的散装实验性质和从头计算。这个配方结合了非相互作用系统的精确自由能与基本测量理论的排斥性贡献和加权密度泛函的短程吸引力的相互作用。我们添加到这些成分的加权极化功能的远程相关的旋转和分子极化率的贡献的介电响应。我们还进行了分子动力学计算空腔形成的自由能和高场介电响应，并表明我们的自由能泛函充分描述了这些属性（这是准确的溶剂化计算的关键）在我们的研究中的所有三种溶剂：水，氯仿和四氯化碳。
英文摘要：
Classical density-functional theory is the most direct approach to equilibrium structures and free energies of inhomogeneous liquids, but requires the construction of an approximate free-energy functional for each liquid of interest. We present a general recipe for constructing functionals for small-molecular liquids based only on bulk experimental properties and ab initio calculations of a single solvent molecule. This recipe combines the exact free energy of the non-interacting system with fundamental measure theory for the repulsive contribution and a weighted density functional for the short-ranged attractive interactions. We add to these ingredients a weighted polarization functional for the long-range correlations in both the rotational and molecular-polarizability contributions to the dielectric response. We also perform molecular dynamics calculations for the free energy of cavity formation and the high-field dielectric response, and show that our free-energy functional adequately describes these properties (which are key for accurate solvation calculations) for all three solvents in our study: water, chloroform and carbon tetrachloride.
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