Classical density-functional theory of inhomogeneous water including explicit molecular structure and nonlinear dielectric response.
Classical density-functional theory of inhomogeneous water including explicit molecular structure and nonlinear dielectric response.
复制标题
非均匀水的经典密度泛函理论，包括显式分子结构和非线性介电响应。
DOI：
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发表时间：
2009
影响因子：
3.3
通讯作者：
Tomás A. Arias
中科院分区：
文献类型：
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作者：
J. Lischner;Tomás A. Arias
我们提出了一个准确的自由能功能的液态水写在一组有效的潜在领域，其中虚构的非相互作用的水分子移动。的功能包含一个精确的表达的熵的非相互作用的分子，从而提供了一个理想的起点，包括复杂的分子间相互作用，这取决于相互作用的分子的取向。我们展示了如何构建一个多余的自由能功能，以重现以下性质的水：介电响应;实验站点站点的相关函数;表面张力;液体的体积模量和该模量随压力的变化;液体和汽相的密度;和液体-蒸汽共存。作为示范，我们提出的结果应用这个理论的行为的液体水在平行板电容器。特别是，我们在非线性制度的水的介电响应的预测，发现良好的协议与已知的数据。
We present an accurate free-energy functional for liquid water written in terms of a set of effective potential fields in which fictitious noninteracting water molecules move. The functional contains an exact expression of the entropy of noninteracting molecules and thus provides an ideal starting point for the inclusion of complex intermolecular interactions which depend on the orientation of the interacting molecules. We show how an excess free-energy functional can be constructed to reproduce the following properties of water: the dielectric response; the experimental site-site correlation functions; the surface tension; the bulk modulus of the liquid and the variation of this modulus with pressure; the density of the liquid and the vapor phase; and liquid-vapor coexistence. As a demonstration, we present results for the application of this theory to the behavior of liquid water in a parallel plate capacitor. In particular, we make predictions for the dielectric response of water in the nonlinear regime, finding excellent agreement with known data.