论文标题
在非常强的平面锚定极限的构造自由度和稳定性的稳定性
Conformational degrees of freedom and stability of splay-bend ordering in the limit of a very strong planar anchoring
论文作者
论文摘要
我们研究了无结构表面上柔性平面三聚体颗粒的自组织。这些分子由两个由间隔器连接的介体单元组成,所有单元均以相同长度相同的硬针头建模。每个分子可以动态地采用两个构象状态:弯曲形状(顺式)和手性曲折(trans-)。 使用恒定压力蒙特卡洛模拟和Onsager型密度函数理论(DFT),我们表明由这些分子组成的系统表现出丰富的(Quasi-)液晶相。最有趣的观察结果是识别稳定的近晶型弯曲($ s_ {sb} $)和手性晶状体A($ S_A^*$)阶段。 $ s_ {sb} $相位也稳定在极限中,仅允许顺式构造器。第二阶段占据相当图的相当一部分是$ s_a^*$带手性层的$ S_A^*$,其中相邻层的手性是相反的。在各个阶段对反式和顺式形式的平均分数的研究表明,尽管在各向同性相中,所有分数均均等,$ s_a^*$相位占主导地位构象体(Zigzag),但Achiral构型在近晶型splay弯曲阶段中赢得了胜利。为了澄清列表splay bend($ n_ {sb} $)阶段的稳定可能性,$ n_ {sb} $和$ s_ {sb} $阶段的自由能在CIS构造中计算在DFT中,用于CIS-CONFormers,用于稳定的密度,显示稳定的密度,显示稳定的$ s_ {SB} $。事实证明,$ n_ {sb} $相位从相转换为列前阶段不稳定,并且其自由能总是高于$ s_ {sb} $的自由能,直到过渡到列前阶段,尽管自由能的差异在接近过渡时的自由能差异极小。
We study the self-organization of flexible planar trimer particles on a structureless surface. The molecules are made up of two mesogenic units linked by a spacer, all of which are modeled as hard needles of the same length. Each molecule can dynamically adopt two conformational states: an achiral bent-shaped (cis-) and a chiral zigzag (trans-) one. Using constant pressure Monte Carlo simulations and Onsager-type density functional theory (DFT), we show that the system consisting of these molecules exhibits a rich spectrum of (quasi-)liquid crystalline phases. The most interesting observation is the identification of stable smectic splay-bend ($S_{SB}$) and chiral smectic A ($S_A^*$) phases. The $S_{SB}$ phase is also stable in the limit, where only cis-conformers are allowed. The second phase occupying a considerable portion of the phase diagram is $S_A^*$ with chiral layers, where the chirality of the neighboring layers is of opposite sign. The study of the average fractions of the trans- and cis-conformers in various phases shows that while in the isotropic phase all fractions are equally populated, the $S_A^*$ phase is dominated by chiral conformers (zigzag), but the achiral conformers win in the smectic splay-bend phase. To clarify the possibility of stabilization of the nematic splay bend ($N_{SB}$) phase for trimers, the free energy of the $N_{SB}$ and $S_{SB}$ phases is calculated within DFT for the cis-conformers, for densities where simulations show stable $S_{SB}$. It turns out that the $N_{SB}$ phase is unstable away from the phase transition to the nematic phase, and its free energy is always higher than that of $S_{SB}$, down to the transition to the nematic phase, although the difference in free energies becomes extremely small when approaching the transition.