Confinement Reveals Hidden Splay-Bend Order in Twist-Bend Nematics

Abstract

Using extensive Monte Carlo (MC) and molecular dynamics (MD) simulations, we investigate how spatial confinement affects molecular organization within thin films of the nematic twist-bend ($\mathrm{N_{TB}}$) phase. Our simulations show that confinement markedly amplifies the otherwise elusive splay-bend order, primarily by suppressing the intrinsic three-dimensional heliconical structure characteristic of bulk $\mathrm{N_{TB}}$. Remarkably, when the $\mathrm{N_{TB}}$ phase is confined between parallel walls imposing planar anchoring, and the bulk wave vector is oriented parallel to the walls, a smectic splay-bend ($\mathrm{S_{SB}}$) phase spontaneously emerges near the confining surfaces. This intermediate structure subsequently transforms into the bulk $\mathrm{N_{TB}}$ phase either directly via a smectic splay-bend-twist ($\mathrm{S_{SBT}}$) phase or through a sequence involving both the $\mathrm{S_{SBT}}$ and the nematic splay-bend-twist ($\mathrm{N_{SBT}}$) phases. Notably, the $\mathrm{N_{SBT}}$ phase becomes particularly pronounced as the molecular bend angle approaches its maximum attainable value in bulk $\mathrm{N_{TB}}$; this regime occurs in close proximity to the $\mathrm{N}\text{--}\mathrm{S_{A}}\text{--}\mathrm{S_{SB}}$ triple point on the bulk phase diagram. Our findings reveal a compelling and intricate interplay among chirality, confinement, and molecular ordering, further evidenced by the calculated elementary director distortions. Crucially, this study opens promising avenues for experimental exploration: confined thin-film geometries serve as powerful model systems for revealing and characterizing novel nematic and smectic liquid-crystal phases that remain elusive in, or currently inaccessible to, bulk experiments.