An official website of the United States government
We have structurally characterized the liquid crystal (LC) phase that can appear as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-y-old void in the taxonomy of smectic LCs and which we term the “smectic Z A ,” is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole–dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic–SmZ A –ferroelectric nematic phase sequence.
more »
« less
Observation of a uniaxial ferroelectric smectic A phase
We report the observation of the smectic A F , a liquid crystal phase of the ferroelectric nematic realm. The smectic A F is a phase of small polar, rod-shaped molecules that form two-dimensional fluid layers spaced by approximately the mean molecular length. The phase is uniaxial, with the molecular director, the local average long-axis orientation, normal to the layer planes, and ferroelectric, with a spontaneous electric polarization parallel to the director. Polarization measurements indicate almost complete polar ordering of the ∼10 Debye longitudinal molecular dipoles, and hysteretic polarization reversal with a coercive field ∼2 × 10 5 V / m is observed. The SmA F phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic (N)–smectic Z A (SmZ A )–ferroelectric nematic (N F )–SmA F phase sequence, and 7N/DIO, exhibiting an N–SmZ A –SmA F phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers.
more »
« less
- Award ID(s):
- 2005170
- PAR ID:
- 10414296
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 119
- Issue:
- 47
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We report the experimental determination of the structure and response to applied electric field of the lower-temperature nematic phase of the previously reported calamitic compound 4-[(4-nitrophenoxy)carbonyl]phenyl2,4-dimethoxybenzoate (RM734). We exploit its electro-optics to visualize the appearance, in the absence of applied field, of a permanent electric polarization density, manifested as a spontaneously broken symmetry in distinct domains of opposite polar orientation. Polarization reversal is mediated by field-induced domain wall movement, making this phase ferroelectric, a 3D uniaxial nematic having a spontaneous, reorientable polarization locally parallel to the director. This polarization density saturates at a low temperature value of ∼6 µC/cm 2 , the largest ever measured for a fluid or glassy material. This polarization is comparable to that of solid state ferroelectrics and is close to the average value obtained by assuming perfect, polar alignment of molecular dipoles in the nematic. We find a host of spectacular optical and hydrodynamic effects driven by ultralow applied field (E ∼ 1 V/cm), produced by the coupling of the large polarization to nematic birefringence and flow. Electrostatic self-interaction of the polarization charge renders the transition from the nematic phase mean field-like and weakly first order and controls the director field structure of the ferroelectric phase. Atomistic molecular dynamics simulation reveals short-range polar molecular interactions that favor ferroelectric ordering, including a tendency for head-to-tail association into polar, chain-like assemblies having polar lateral correlations. These results indicate a significant potential for transformative, new nematic physics, chemistry, and applications based on the enhanced understanding, development, and exploitation of molecular electrostatic interaction.more » « less
-
Abstract The dynamics of swimming bacteria depend on the properties of their habitat media. Recently it is shown that the motion of swimming bacteria dispersed directly in a non‐toxic water‐based lyotropic chromonic liquid crystal can be controlled by the director field of the liquid crystal. Here, we investigate whether the macroscopic polar order of a ferroelectric nematic liquid crystal (NF) can be recognized by bacteria B. Subtilis swimming in a water dispersion adjacent to a glassy NFfilm by surface interactions alone. Our results show that B. Subtilis tends to move in the direction antiparallel to the spontaneous electric polarization at the NFsurface. Their speed is found to be the same with or without a polar NFlayer. In contrast to observation on crystal ferroelectric films, the bacteria do not get immobilized. These observations may offer a pathway to creation of polar microinserts to direct bacterial motion in vivo.more » « less
-
We show that surface interactions can vectorially structure the three-dimensional polarization field of a ferroelectric fluid. The contact between a ferroelectric nematic liquid crystal and a surface with in-plane polarity generates a preferred in-plane orientation of the polarization field at that interface. This is a route to the formation of fluid or glassy monodomains of high polarization without the need for electric field poling. For example, unidirectional buffing of polyimide films on planar surfaces to give quadrupolar in-plane anisotropy also induces macroscopic in-plane polar order at the surfaces, enabling the formation of a variety of azimuthal polar director structures in the cell interior, including uniform and twisted states. In a π-twist cell, obtained with antiparallel, unidirectional buffing on opposing surfaces, we demonstrate three distinct modes of ferroelectric nematic electro-optic response: intrinsic, viscosity-limited, field-induced molecular reorientation; field-induced motion of domain walls separating twisted states of opposite chirality; and propagation of polarization reorientation solitons from the cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in antiparallel-rubbed cells produce Grandjean textures of helical twist that can be unwound via field-induced polar surface reorientation transitions. Fields required are in the 3-V/mm range, indicating an in-plane polar anchoring energy of w P ∼3 × 10 −3 J/m 2 .more » « less
-
Elastic constants of splay K_11, twist K_22, and bend K_33 of nematic liquid crystals are often assumed to be equal to each other in order to simplify the theoretical description of complex director fields. Here we present examples of how the disparity of K_11 and K_33 produces effects that cannot be described in a one-constant approximation. In a lyotropic chromonic liquid crystal, nematic droplets coexisting with the isotropic phase change their shape from a simply-connected tactoid to a topologically distinct toroid as a result of temperature or concentration variation. The transformation is caused by the increase of the splay-to-bend ratio K_11/K_33. A phase transition from a conventional nematic to a twist-bend nematic implies that the ratio K_11/K_33 changes from very large to very small. As a result, the defects caused by an externally applied electric field change the deformation mode of optic axis from bend to splay. In the paraelectric-ferroelectric nematic transition, one finds an inverse situation: K_11/K_33 changes from small to large, which shapes the domain walls in the spontaneous electric polarization field as conic sections. The polarization field tends to be solenoidal, or divergence-free, a behavior complementary to irrotational curl-free director textures of a smectic A.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2210062119
