论文标题

自由旋转多分散的立方体的自组装:揭示双轴列相的边界

Self-assembly of Freely-rotating Polydisperse Cuboids: Unveiling the Boundaries of the Biaxial Nematic Phase

论文作者

Rafael, Effran Mirzad, Corbett, Daniel, Cuetos, Alejandro, Patti, Alessandro

论文摘要

胶体立方体有可能自组装成双轴液晶阶段,这些液晶相表现出两个独立的光轴。在过去的几十年中,几项理论著作预测了相图的广泛区域,在该区域中,双轴列相思是稳定的,但对粒子旋转自由度施加了相当强的约束。在这项工作中,我们采用分子模拟来研究尺寸分散性对自由旋转硬立方体的相行为的影响,在这里以自偶形纳米棒为模型。已经提出,这种特殊的各向异性恰好在扁平和倾斜的几何形状之间,是促进双轴性相位的最合适的。我们观察到大小分散性从根本上改变了单分散系统的相行为,并导致形成难以捉摸的双轴列相位,这在包装分数的大区域与多分散相图。尽管我们的结果证实了在过去的实验观察结果中报道的关于略微质量的对小铁矿颗粒的胶体分散体的趋势,但它们无法再现这些实验中观察到的直接各向同性到双轴列相变的趋势。

Colloidal cuboids have the potential to self-assemble into biaxial liquid crystal phases, which exhibit two independent optical axes. Over the last few decades, several theoretical works predicted the existence of a wide region of the phase diagram where the biaxial nematic phase would be stable, but imposed rather strong constraints on the particle rotational degrees of freedom. In this work, we employ molecular simulation to investigate the impact of size dispersity on the phase behaviour of freely-rotating hard cuboids, here modelled as self-dual-shaped nanoboards. This peculiar anisotropy, exactly in between oblate and prolate geometry, has been proposed as the most appropriate to promote phase biaxiality. We observe that size dispersity radically changes the phase behaviour of monodisperse systems and leads to the formation of the elusive biaxial nematic phase, being found in an large region of the packing fraction vs polydispersity phase diagram. Although our results confirm the tendencies reported in past experimental observations on colloidal dispersions of slightly prolate goethite particles, they cannot reproduce the direct isotropic-to-biaxial nematic phase transition observed in these experiments.

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