Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, USA.
J Chem Phys. 2014 Jan 14;140(2):024703. doi: 10.1063/1.4858433.
Using molecular-dynamics simulation and Gibbs-Cahn Integration, we calculate the interfacial free energy γ of a binary hard-sphere fluid mixture at a structureless, planar hard wall. The calculation is performed as a function of packing fraction (density) for several values of the diameter ratio α = σ2∕σ1, where σ1 and σ2 are the diameters of the two particle types in the mixture. Our results are compared to those obtained from the bulk version of the White Bear Mark II (WBII) classical density-functional theory, which is a modification of the Fundamental-Measure Theory of Rosenfeld. The WBII bulk theory is shown to be in very good agreement with the simulation results, with significant deviation only at the very highest packing fractions.
利用分子动力学模拟和 Gibbs-Cahn 积分，我们计算了无定形、平面硬壁上二元硬球流体混合物的界面自由能 γ。该计算作为几种直径比 α = σ2∕σ1 的 packing fraction（密度）的函数进行，其中 σ1 和 σ2 是混合物中两种颗粒类型的直径。我们的结果与从 White Bear Mark II（WBII）经典密度泛函理论的本体版本得到的结果进行了比较，该理论是 Rosenfeld 的基本测量理论的修正。WBII 本体理论与模拟结果非常吻合，只有在最高 packing fraction 时才会出现显著偏差。
