Theoretische Chemie, Universität Duisburg-Essen, D-45141 Essen, Germany.
Soft Matter. 2018 Nov 14;14(44):8962-8973. doi: 10.1039/c8sm01790e.
We explore length segregation in binary mixtures of spherocylinders of lengths L1 and L2 which are tangentially confined on a spherical surface of radius R. The orientation of the spherocylinders is constrained along an externally imposed direction field on the sphere which is either along the longitude or the latitude lines of the sphere. In both situations, integer orientational defects at the poles are imposed. Using computer simulations we show that these topological defects induce a complex segregation picture also depending on the length ratio factor γ = L2/L1 and the total packing fraction η of the spherocylinders. When the binary mixture is aligned along the longitude lines of the sphere, shorter rods tend to accumulate at the topological defects of the polar caps whereas longer rods occupy the central equatorial area of the spherical surface. In the reverse case of latitude ordering, a new state can emerge where longer rods are predominantly both in the cap and in the equatorial areas and shorter rods are localized in between. As a reference situation, we consider a defect-free situation in the flat plane and do not find any length segregation there at similar γ and η; hence, the segregation is purely induced by the imposed topological defects. We also develop an Onsager-like density functional theory which is capable of predicting length segregation in ordered mixtures. At low density, the results of this theory are in good agreement with the simulation data.
我们研究了长度为 L1 和 L2 的各向异性圆柱体在切向约束于半径为 R 的球面上的二元混合物中的长度分离。圆柱体的方向沿着球面上的外部强制方向场限制,该方向场可以沿着球的经度线或纬度线。在这两种情况下,在极点处都施加整数取向缺陷。通过计算机模拟,我们表明,这些拓扑缺陷也会导致复杂的分离图,这取决于长度比因子 γ = L2/L1 和各向异性圆柱体的总堆积分数 η。当二元混合物沿着球的经度线排列时,较短的棒趋于在极帽的拓扑缺陷处积累,而较长的棒占据球表面的赤道中心区域。在纬度排序的相反情况下,可能会出现一种新状态,其中较长的棒主要存在于帽中和赤道区域,而较短的棒则集中在两者之间。作为参考情况,我们考虑了无缺陷的平面情况,在类似的 γ 和 η 下,那里没有发现任何长度分离;因此,分离完全是由施加的拓扑缺陷引起的。我们还开发了一种类似于 Onsager 的密度泛函理论,该理论能够预测有序混合物中的长度分离。在低密度下,该理论的结果与模拟数据吻合良好。