Physique des Liquides et Milieux Complexes, Faculté des Sciences et Technologie, Université Paris-Est (Créteil), 61 Av. du Général de Gaulle, 94010 Créteil Cedex, France.
J Phys Chem B. 2010 Dec 23;114(50):16824-31. doi: 10.1021/jp107157a. Epub 2010 Nov 23.
The structure of a binary mixture of nonadditive hard spheres confined in a slit pore is studied by the integral equations method in which the confining medium acts as a giant particle at infinite dilution. The adsorption/desorption curves are studied as a function of the composition and density, when the homogeneous bulk mixture is near the demixing instability. The Ornstein-Zernike integral equations are solved with the reference functional approximation closure in which the bridge functions are derived from Rosenfeld's hard sphere functional for additive hard sphere. To study the high composition asymmetry regime in which a population inversion occurs, we developed an approximate closure that overcomes the no solution problem of the integral equation. By comparison with simulation data, this method is shown to be sufficiently accurate for predicting the threshold density for the population inversion. The predictions of simpler closure relations are briefly examined.
本文采用积分方程方法研究了受限在狭缝孔中具有非加和硬球性质的二元混合物的结构，其中受限介质在无限稀释时表现为巨大粒子。研究了吸附/解吸曲线作为组成和密度的函数，当均相本体混合物接近离析不稳定性时。采用参考函数逼近法求解奥恩斯坦-泽尔尼克积分方程，其中桥函数由罗森菲尔德加和硬球的硬球泛函导出。为了研究发生种群反转的高组成不对称性区域，我们开发了一种近似封闭方法，该方法克服了积分方程无解的问题。通过与模拟数据的比较，表明该方法对于预测种群反转的阈值密度是足够准确的。还简要考察了更简单的封闭关系的预测。
