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基于密度泛函理论的二元硬片混合物的体相行为

Bulk phase behavior of binary hard platelet mixtures from density functional theory.

作者信息

Phillips Jonathan, Schmidt Matthias

机构信息

H.H. Wills Physics Laboratory, Bristol University, Royal Fort, Tyndall Avenue, Bristol BS8 1TL, United Kingdom.

出版信息

Phys Rev E Stat Nonlin Soft Matter Phys. 2010 Apr;81(4 Pt 1):041401. doi: 10.1103/PhysRevE.81.041401. Epub 2010 Apr 8.

Abstract

We investigate isotropic-isotropic, isotropic-nematic, and nematic-nematic phase coexistence in binary mixtures of circular platelets with vanishing thickness, continuous rotational degrees of freedom, and radial size ratios lambda up to 5. A fundamental measure density functional theory, previously used for the one-component model, is presented and results are compared against those from Onsager theory as a benchmark. For lambda<or=1.7 the system displays isotropic-nematic phase coexistence with a widening of the biphasic region for increasing values of lambda . For size ratios lambda>or=2, we find that demixing into two nematic states becomes stable and an isotropic-nematic-nematic triple point can occur. Fundamental measure theory gives a smaller isotropic-nematic biphasic region than Onsager theory and locates the transition at lower densities. Furthermore, nematic-nematic demixing occurs over a larger range of compositions at a given value of lambda than found in Onsager theory. Both theories predict the same topologies of the phase diagrams. The partial nematic order parameters vary strongly with composition and indicate that the larger particles are more strongly ordered than the smaller particles.

摘要

我们研究了厚度可忽略不计、具有连续旋转自由度且径向尺寸比λ高达5的圆形薄片二元混合物中的各向同性-各向同性、各向同性-向列相和向列相-向列相共存情况。提出了一种先前用于单组分模型的基本度量密度泛函理论,并将结果与作为基准的昂萨格理论的结果进行了比较。对于λ≤1.7,系统呈现各向同性-向列相共存,随着λ值的增加,双相区域变宽。对于尺寸比λ≥2,我们发现分离成两个向列相状态变得稳定,并且可能出现各向同性-向列相-向列相三相点。基本度量理论给出的各向同性-向列相双相区域比昂萨格理论的小,并且在较低密度下确定转变。此外,在给定的λ值下,向列相-向列相分离发生的组成范围比昂萨格理论中的更大。两种理论都预测了相图的相同拓扑结构。部分向列相序参量随组成变化强烈,表明较大颗粒比较小颗粒的有序程度更高。

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