An accurate theoretical description of fluids composed of fully anisotropic molecules: Application to C2v symmetry
An accurate theoretical description of fluids composed of fully anisotropic molecules: Application to C2v symmetry
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由完全各向异性分子组成的流体的准确理论描述：在 C2v 对称性中的应用
DOI：
10.1063/1.474825
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发表时间：
1997
影响因子：
4.4
通讯作者：
C. Martín
中科院分区：
文献类型：
--
作者：
M. Alvarez;F. Lado;E. Lomba;M. Lombardero;C. Martín
我们使用两个分子积分方程近似来计算由具有 C2v 对称性的平面分子（即 SO2 和 H2S）组成的两种液体的热力学性质和微观结构。这些近似将精确的分子 Ornstein-Zernike 方程与超网链 (HNC) 和参考超网链 (RHNC) 闭包结合起来。针对各种热力学状态获得的理论结果与分子动力学计算非常吻合。特别是，原子-原子分布函数得到了很好的再现。我们发现，使用硬球流体参考系统的 RHNC 近似在压力计算方面比 HNC 具有显着的改进。我们还包括自洽平均场计算，以纳入极化率对液体 SO2 介电常数的影响。该数量的最终结果与实验值非常吻合。相比之下，用于 H2S 静电相互作用的模型会导致异常……
We use two molecular integral equation approximations to compute the thermodynamic properties and microscopic structure of two liquids composed of planar molecules with C2v symmetry, namely SO2 and H2S. These approximations couple the exact molecular Ornstein–Zernike equation with the hypernetted chain (HNC) and reference-hypernetted chain (RHNC) closures. The theoretical results obtained for various thermodynamic states agree remarkably well with molecular dynamics calculations. In particular, the atom-atom distribution functions are very well reproduced. We find that the RHNC approximation with a hard-sphere fluid reference system offers notable improvement over HNC in the pressure calculation. We include also a self-consistent mean field calculation to incorporate the effect of polarizability on the dielectric constant of liquid SO2. Final results for this quantity are in excellent agreement with experimental values. In contrast, the model used for the electrostatic interactions in H2S leads to anomalo...