Incommensurate phase in Λ-cobalt (III) sepulchrate trinitrate governed by highly competitive N–H···O and C–H···O hydrogen bond networks

Phase transitions in molecular crystals are often determined by intermolecular interactions. The cage complex of [Co(C12H30N8)]3+·3NO3– is reported to undergo a disorder–order phase transition at Tc1 ≈ 133 K upon cooling. Temperature-dependent neutron and synchrotron diffraction experiments revealed satellite reflections in addition to main reflections in the diffraction patterns below Tc1. The modulation wave vector varies as function of temperature and locks in at Tc3 ≈ 98 K. Here, we demonstrate that the crystal symmetry lowers from hexagonal to monoclinic in the incommensurately modulated phases in Tc1 ˂ T ˂ Tc3. Distinctive levels of competitions: trade-off between longer N–H···O and shorter C–H···O hydrogen bonds; steric constraints to dense C-H···O bonds give rise to pronounced modulation of the basic structure. Severely frustrated crystal packing in the incommensurate phase is precursor to optimal balance of intermolecular interactions in the lock-in phase.

Director Deformations, Geometric Frustration, and Modulated Phases in Liquid Crystals

This article analyzes modulated phases in liquid crystals, from the long-established cholesteric and blue phases to the recently discovered twist-bend, splay-bend, and splay nematic phases, as well as the twist-grain-boundary (TGB) and helical nanofilament variations on smectic phases. The analysis uses the concept of four fundamental modes of director deformation: twist, bend, splay, and a fourth mode related to saddle-splay. Each mode is coupled to a specific type of molecular order: chirality, polarization perpendicular and parallel to the director, and octupolar order. When the liquid crystal develops one type of spontaneous order, the ideal local structure becomes nonuniform, with the corresponding director deformation. In general, the ideal local structure is frustrated; it cannot fill space. As a result, the liquid crystal must form a complex global phase, which may have a combination of deformation modes, and may have a periodic array of defects. Thus, the concept of an ideal local structure under geometric frustration provides a unified framework to understand the wide variety of modulated phases. Expected final online publication date for the Annual Review of Condensed Matter Physics, Volume 13 is March 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Nanoscale bubble domains with polar topologies in bulk ferroelectrics

Multitudinous topological configurations spawn oases of many physical properties and phenomena in condensed-matter physics. Nano-sized ferroelectric bubble domains with various polar topologies (e.g., vortices, skyrmions) achieved in ferroelectric films present great potential for valuable physical properties. However, experimentally manipulating bubble domains has remained elusive especially in the bulk form. Here, in any bulk material, we achieve self-confined bubble domains with multiple polar topologies in bulk Bi0.5Na0.5TiO3 ferroelectrics, especially skyrmions, as validated by direct Z-contrast imaging. This phenomenon is driven by the interplay of bulk, elastic and electrostatic energies of coexisting modulated phases with strong and weak spontaneous polarizations. We demonstrate reversable and tip-voltage magnitude/time-dependent donut-like domain morphology evolution towards continuously and reversibly modulated high-density nonvolatile ferroelectric memories.

A generalized density-modulated twist-splay-bend phase of banana-shaped particles

In 1976, Meyer predicted that bend distortions of the nematic director field are complemented by deformations of either twist or splay, yielding twist-bend and splay-bend nematic phases, respectively. Four decades later, the existence of the splay-bend nematic phase remains dubious, and the origin of these spontaneous distortions uncertain. Here, we conjecture that bend deformations of the nematic director can be complemented by simultaneous distortions of both twist and splay, yielding a twist-splay-bend nematic phase. Using theory and simulations, we show that the coupling between polar order and bend deformations drives the formation of modulated phases in systems of curved rods. We find that twist-bend phases transition to splay-bend phases via intermediate twist-splay-bend phases, and that splay distortions are always accompanied by periodic density modulations due to the coupling of the particle curvature with the non-uniform curvature of the splayed director field, implying that the twist-splay-bend and splay-bend phases of banana-shaped particles are actually smectic phases.

Nanoscale bubble domains with polar topologies in bulk ferroelectrics

Multitudinous topological configurations spawn new oases of novel phenomena and physical properties in condensed-matter physics1. Nano-sized ferroelectric bubble domains with various polar topologies (e.g., vortices, skyrmions) achieved in ferroelectric films present great potential for valuable physical properties2–5. However, experimentally manipulating bubble domains has remained elusive especially in the bulk form. Here, for the first time in any bulk material, we achieve self-confined bubble domains with multiple polar topologies in bulk Bi0.5Na0.5TiO3 ferroelectrics, especially skyrmions, as validated by direct Z-contrast imaging. This phenomenon is driven by the interplay of bulk, elastic and electrostatic energies of coexisting modulated phases with strong and weak spontaneous polarizations. We demonstrate reversable and tip-voltage magnitude/time-dependent donut-like domain morphology evolution towards continuously and reversibly modulated high-density nonvolatile ferroelectric memories.