Conformational degrees of freedom and stability of splay-bend ordering in the limit of a very strong planar anchoring

TL;DR

This study combines simulations and density functional theory to explore the phase behavior of flexible trimer molecules with conformational flexibility, revealing stable splay-bend and chiral smectic phases influenced by molecular conformations.

Contribution

It introduces a detailed analysis of conformational effects on liquid crystalline phases of trimers, identifying stable splay-bend and chiral smectic phases under strong planar anchoring conditions.

Findings

Stable splay-bend ($S_{SB}$) phase identified in simulations and theory.

Chiral smectic A ($S_A^*$) phase with alternating chirality observed.

Free energy calculations show $N_{SB}$ phase is unstable compared to $S_{SB}$.

Abstract

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.