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硬片、棒和球的胶体混合物的密度泛函理论。

Density functional theory for colloidal mixtures of hard platelets, rods, and spheres.

作者信息

Esztermann Ansgar, Reich Hendrik, Schmidt Matthias

机构信息

Institut für Theoretische Physik II, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany.

出版信息

Phys Rev E Stat Nonlin Soft Matter Phys. 2006 Jan;73(1 Pt 1):011409. doi: 10.1103/PhysRevE.73.011409. Epub 2006 Jan 25.

Abstract

A geometry-based density-functional theory is presented for mixtures of hard spheres, hard needles, and hard platelets; both the needles and platelets are taken to be of vanishing thickness. Geometrical weight functions that are characteristic for each species are given, and it is shown how convolutions of pairs of weight functions recover each Mayer bond of the ternary mixture and hence ensure the correct second virial expansion of the excess free-energy functional. The case of sphere-platelet overlap relies on the same approximation as does Rosenfeld's functional for strictly two-dimensional hard disks. We explicitly control contributions to the excess free energy that are of third order in density. Analytic expressions relevant for the application of the theory to states with planar translational and cylindrical rotational symmetry--e.g., to describe behavior at planar smooth walls--are given. For binary sphere-platelet mixtures, in the appropriate limit of small platelet densities, the theory differs from that used in a recent treatment [L. Harnau and S. Dietrich, Phys. Rev. E 71, 011504 (2004)]. As a test case of our approach we consider the isotropic-nematic bulk transition of pure hard platelets, which we find to be weakly first order, with values for the coexistence densities and the nematic order parameter that compare well with simulation results.

摘要

本文提出了一种基于几何的密度泛函理论,用于硬球、硬针和硬片混合物;针和片的厚度均视为零。给出了每种粒子特有的几何权重函数,并展示了权重函数对的卷积如何恢复三元混合物的每个迈耶键,从而确保过量自由能泛函的正确第二维里展开。球 - 片重叠的情况依赖于与罗森菲尔德针对严格二维硬磁盘的泛函相同的近似。我们明确控制了对过量自由能的三阶密度贡献。给出了与该理论应用于具有平面平移和圆柱旋转对称性的状态(例如描述平面光滑壁处的行为)相关的解析表达式。对于二元球 - 片混合物,在片密度较小的适当极限下,该理论与最近一篇论文[L. 哈瑙和 S. 迪特里希,《物理评论E》71,011504(2004)]中使用的理论不同。作为我们方法的一个测试案例,我们考虑了纯硬片的各向同性 - 向列相 bulk 转变,发现它是弱一级相变,其共存密度和向列序参数的值与模拟结果相当。

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