Samulski Edward T, Reyes-Arango Denisse, Vanakaras Alexandros G, Photinos Demetri J
Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599-3290, USA.
Department of Materials Science, University of Patras, 26504 Patras, Greece.
Nanomaterials (Basel). 2021 Dec 29;12(1):93. doi: 10.3390/nano12010093.
The nature of the nanoscale structural organization in modulated nematic phases formed by molecules having a nonlinear molecular architecture is a central issue in contemporary liquid crystal research. Nevertheless, the elucidation of the molecular organization is incomplete and poorly understood. One attempt to explain nanoscale phenomena merely "shrinks down" established macroscopic continuum elasticity modeling. That explanation initially (and mistakenly) identified the low temperature nematic phase (), first observed in symmetric mesogenic dimers of the CB--CB series with an odd number of methylene spacers (), as a twist-bend nematic (). We show that the is unrelated to any of the elastic deformations (bend, splay, twist) stipulated by the continuum elasticity theory of nematics. Results from molecular theory and computer simulations are used to illuminate the local symmetry and physical origins of the nanoscale modulations in the phase, a spontaneously chiral and locally polar nematic. We emphasize and contrast the differences between the and theoretically conceivable nematics exhibiting spontaneous modulations of the elastic modes by presenting a coherent formulation of one-dimensionally modulated nematics based on the Frank-Oseen elasticity theory. The conditions for the appearance of nematic phases presenting true elastic modulations of the twist-bend, splay-bend, etc., combinations are discussed and shown to clearly exclude identifications with the nanoscale-modulated nematics observed experimentally, e.g., the phase. The latter modulation derives from packing constraints associated with nonlinear molecules-a chiral, locally-polar structural organization indicative of a new type of nematic phase.
由具有非线性分子结构的分子形成的调制向列相中的纳米级结构组织的本质是当代液晶研究中的一个核心问题。然而,对分子组织的阐明并不完整且了解甚少。一种解释纳米级现象的尝试仅仅是将已有的宏观连续介质弹性模型“缩小”。该解释最初(且错误地)将在具有奇数个亚甲基间隔基的CB - CB系列对称介晶二聚体中首次观察到的低温向列相(),识别为扭曲弯曲向列相()。我们表明,该相与向列相连续介质弹性理论规定的任何弹性变形(弯曲、展曲、扭曲)均无关。分子理论和计算机模拟的结果被用于阐明该相(一种自发手性和局部极性向列相)中纳米级调制的局部对称性和物理起源。我们通过基于弗兰克 - 奥森弹性理论提出一维调制向列相的连贯表述,强调并对比了该相与理论上可想象的表现出自发弹性模式调制的向列相之间的差异。讨论了呈现扭曲 - 弯曲、展曲 - 弯曲等组合的真正弹性调制的向列相出现的条件,并表明这些条件明确排除了与实验观察到的纳米级调制向列相(例如该相)的等同性。后者的调制源于与非线性分子相关的堆积限制——一种指示新型向列相的手性、局部极性结构组织。