Nematic twist-bend phase of a bent liquid crystal dimer: field-induced deformations of the helical structure, macroscopic polarization and fast switching speeds
Sourav Patranabish, Aloka Sinha, Madhu B. Kanakala, Channabasaveshwar V. Yelamaggad
The twist-bend nematic (Ntb) phase is a recent addition to the nematic (N) phases of liquid crystals (LCs). A net polar order in the Ntb phase under an external electric field was predicted in several recent theoretical studies but yet to be experimentally realized. We investigated the polar nature, dielectric properties, electro-optical switching and optical transmission properties of a bent LC dimer CB7CB. The LC showed a relatively high-temperature nematic (N) phase and a lower-temperature nematic (NX) phase (also called Ntb in literature). A threshold-dependent polarization current response with large polarization values was obtained in the entire mesophase range. The associated switching times were found in sub-millisecond region. This ferroelectric-like polarization resulted from collective reorientation of polar cybotactic clusters. In NX phase, electric field-induced deformation of twisted helical structures also contributed to net polarization. Dielectric measurements confirmed the presence of cybotactic clusters via relaxation processes with large activation energies. Deformation of the NX helical structure under external electric field was corroborated by polarized optical microscopy and optical transmission studies. The field-induced deformations, net polar order and fast switching will contribute towards greater understanding of the NX (or Ntb) phase dynamics. It may also find applications in next-generation electro-optic devices.
We studied the correlation between the molecular structure and the formation of helical nanofilaments (HNFs) of bent-core dimeric molecules with varying linkage lengths. To obtain precise structural data, a single domain of HNFs was prepared under physical confinement using porous 1D nanochannels, made up of anodic aluminium oxide films. Electron microscopy and grazing incidence X-ray diffraction were used to elucidate the linkage length-dependent formation of HNFs.
We develop a Landau theory for bend flexoelectricity in liquid crystals of bent-core molecules. In the nematic phase of the model, the bend flexoelectric coefficient increases as we reduce the temperature toward the nematic to polar phase transition. At this critical point, there is a second order transition from high-temperature uniform nematic phase to low-temperature nonuniform polar phase composed of twist-bend or splay-bend deformations. To test the predictions of Landau theory, we perform Monte Carlo simulations to find the director and polarization configurations as functions of tempera…
How change in molecular structure can affect relative stability and structural properties of the twist-bend nematic phase (N$_\text{TB}$)? Here we extend the mean-field model [C. Greco et al., Soft Matter, 2014, 10, 9318] for bent-shaped achiral molecules, to study the influence of arm molecular biaxiality and the value of molecule's bend angle on relative stability of N$_\text{TB}$. In particular we show that by controlling biaxiality of molecule's arms up to four ordered phases can become stable. They involve locally uniaxial and biaxial variants of N$_\text{TB}$, together with the uniaxial …
Binary mixtures of the twist-bend nematic-forming liquid crystal CB7CB with the prototypical rod-like liquid crystal 5CB exhibit a twist-bend nematic phase with properties similar to those reported for neat CB7CB. The mixtures appear homogeneous, with no micron- or nano-scale segregation evident at any concentration. The linear dependence of the phase transition temperature on concentration indicates that these binary mixtures are nearly ideal. However, a decrease in the viscosity with the addition of 5CB allows the characteristic twist-bend stripe textures to relax into a state of uniform bir…
We have numerically studied a liquid composed of achiral, bent-shaped molecules built of tangent spheres. The system is known to spontaneously break mirror symmetry, as it forms a macroscopically chiral, twist-bend nematic phase [Phys. Rev. Lett. 115, 147801 (2015)]. Here, we have examined the full phase diagram of such liquid and observed several phases characterized by orientational and/or translational ordering of molecules. Apart from conventional nematic, smectic A, and the above-mentioned twist-bend nematic phase, we have identified antiferroelectric smectic A phase. For large densities …
The chiral, heliconical (twist-bend) nematic ground state is reported in an achiral, rigid, bent-core mesogen (UD68). Similar to the nematic twist-bend (NTB) phase observed in bent molecular dimers, the NTB phase of UD68 forms macroscopic, smectic-like focal-conic textures and exhibits nanoscale, periodic modulation with no associated modulation of the electron density, i.e., without a detectable lamellar x-ray reflection peak. The NTB helical pitch is pTB ~ 14 nm. When an electric field is applied normal to the helix axis, a weak electroclinic effect is observed, revealing 50 um-scale left- a…
Dielectric spectroscopy of a twist bend nematic phase of an achiral bent core liquid crystalline compound under DC bias is used to investigate its response to electric field. Two collective relaxation processes are revealed, these are assigned to distortions of helicoidal structure by the external bias field. Frequency of the mode depends primarily on the helicoidal angle and has anomalous, softening- like behaviour at the nematic to the twist bend nematic transition. A coupling of dielectric anisotropy with electric field gives rise to a new equilibrium periodic structure in the time scale in…
Spontaneous formation of polarization gratings by liquid crystals made of bent dimeric molecules is reported. The grating is formed within the temperature range of the twist bend modulated nematic phase, NTB, without the necessity to pattern the cell surfaces, therefore the modulated nematic phase is a promising candidate for low-cost modulators and beam steering devices, the polarization properties of which can be tuned by temperature. In addition, the study of the diffracted light properties turns out to be a sensitive measuring technique for determination of the 3D spatial variation of the …
The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered macroscopically chiral heliconical winding of molecular scale pitch, in absence of positional ordering. Here we characterize the structure of the ground state of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB over a wide range of concentrations and temperatures, showing that the contour length along the molecular direction for a single turn of the helix is approximately equal to 2πRmol, where Rmol is the radius of bend cu…
Periodic structures of phases with orientational order of molecules, but homogenous electron density distribution: a short pitch cholesteric, blue phase and twist-bend nematic phase, were probed by a resonant soft x-ray scattering (RSoXS) at the carbon K-edge. The theoretical model shows that in case of a simple heliconical nematic structure two resonant signals corresponding to the full and half pitch band should be present, while only the full pitch band is observed in experiment. This suggests that the twist-bend nematic phase has complex structure with a double-helix, built of two interloc…
By means of extensive replica-exchange simulations of generic coarse-grained models for helical polymers, we systematically investigate the structural transitions into all possible helical phases for flexible and semiflexible elastic polymers with self-interaction under the influence of torsion barriers. The competing interactions lead to a variety of conformational phases including disordered helical arrangements, single helices, and ordered, tertiary helix bundles. Most remarkably, we find that a bending restraint entails a clear separation and stabilization of the helical phases. This aids …
The ground state of twist-bend nematic liquid crystals is a heliconical molecular arrangement in which the nematic director precesses uniformly about an axis, making a fixed angle with it. Both precession senses are allowed in the ground state of these phases. When one of the two \emph{helicities} is prescribed, a single helical nematic phase emerges. A quadratic elastic theory is proposed here for each of these phases which features the same elastic constants as the classical theory of the nematic phase, requiring all of them to be positive. To describe the helix axis, it introduces an extra …
Recent work indicates that twist-bend coupling plays an important role in DNA micromechanics. Here we investigate its effect on bent DNA. We provide an analytical solution of the minimum-energy shape of circular DNA, showing that twist-bend coupling induces sinusoidal twist waves. This solution is in excellent agreement with both coarse-grained simulations of minicircles and nucleosomal DNA data, which is bent and wrapped around histone proteins in a superhelical conformation. Our analysis shows that the observed twist oscillation in nucleosomal DNA, so far attributed to the interaction with t…
We demonstrate that nature has produced a close-packed helical twisted filamentous material in the biomineralization of the mollusc. In liquid crystals, twist-bend nematics have been predicted and observed. We present and analyse evidence that the helical biomineral microstructure of mollusc shells may be formed from such a liquid-crystal precursor.
The strong bending of polymers is poorly understood. We propose a general quantitative framework of polymer bending that includes both the weak and strong bending regimes on the same footing, based on a single general physical principle. As the bending deformation increases beyond a certain (polymer-specific) point, the change in the convexity properties of the effective bending energy of the polymer makes the harmonic deformation energetically unfavorable: in this strong bending regime the energy of the polymer varies linearly with the average bending angle as the system follows the convex hu…
The recently discovered twist-bend nematic phase, $\rm N_{tb}$, is a non-uniform equilibrium nematic phase that presents a spontaneous bend with a precession of the nematic director, $\textbf{n}$, on a conical helix with a tilt angle $θ$ and helical pitch $P$. The stability of the $\rm N_{tb}$ phase has been recently demonstrated from the elastic point of view by extending the Frank elastic energy density of the nematic phase to include the symmetry element of helical axis, $\bf t$. In the present communication, we investigate the influence of an external bulk field (magnetic or electric) on t…
Two-dimensional ensembles of bent-core shaped molecules attain at highly orienting surfaces liquid crystalline structures characteristic mostly for lamellar chiral or nonchiral antiferroelectric order. Here, using the Onsager-type of density functional theory supplemented by constant-pressure Monte-Carlo (MC) simulation we investigate the role of excluded-volume interactions in stabilizing different structures in monolayers filled with bent-shaped molecules. We study influence of molecular features, like the apex angle, thickness of the arm and the type of the arm edges on the stability of lay…
Liquid crystalline systems exhibiting both macroscopic chirality and smectic order experience frustration resulting in mesophases possessing complex three-dimensional order. In the twist-grain-boundary phase, defect lattices mediate the propagation of twist throughout the system. We propose a new chiral smectic structure composed of a lattice of chiral bundles as a model of the helical nanofilament (B4) phase of bent core smectics.
We synthesized the liquid crystal dimer and trimer members of a series of flexible linear oligomers and characterized their microscopic and nanoscopic properties using resonant soft x-ray scattering and a number of other experimental techniques. On the microscopic scale, the twist-bend phases of the dimer and trimer appear essentially identical. However, while the liquid crystal dimer exhibits a temperature-dependent variation of its twist-bend helical pitch varying from 100 - 170 Å on heating, the trimer exhibits an essentially temperature-independent pitch of 66 Å, significantly shorter than…
A novel light-sensitive chiral dopant ChD-3816 (an azo compound containing 4-hexanoyloxyphenyl and 2-isopropyl-5-methylcyclohexylbenzoate moieties) was used for inducing helical twisting in Ntb-forming mixtures of CB7CB/CB6OCB with 5CB added to decrease the phase transition temperatures. The effects of ChD-3816 upon phase transition temperatures, as well as effects of its concentration on the measured values of helical twisting were determined. Most of the measured parameters could be varied due to light-induced trans-cis isomerization of ChD-3816. Under electric field, selective reflection sp…
It has been known that at high density, the local orientation of banana-shaped molecules shows a spontaneously bent state, giving rise to interesting liquid-crystalline phases such as splay-bend and twist-bend. This spontaneous bend can be modelled theoretically by allowing the bend elastic constant in the Frank elastic energy to become negative. Here we extend this idea to polar banana and pizza-slice-shaped molecules which can also splay spontaneously. By allowing both splay and bend elastic constants to be negative we discovered two additional new liquid crystalline phases. In particular, u…
We introduce a simple geometric model for a double-stranded and double-helical polymer. We study the statistical mechanics of such polymers using both analytical techniques and simulation. Our model has a single energy-scale which determines both the bending and twisting rigidity of the polymer. The helix melts at a particular temperature T_c below which the chain has a helical structure and above which this structure is disordered. Under extension we find that for small forces, the behaviour is very similar to worm-like chain behaviour but becomes very different at higher forces.
By combining analytical results and simulations of various coarse-grained models we investigate the minimal energy shape of DNA minicircles which are torsionally constrained by an imposed over or undertwist. We show that twist-bend coupling, a cross interaction term discussed in the recent DNA literature, induces minimal energy shapes with a periodic alternance of parts with high and low curvature resembling rounded polygons. We briefly discuss the possible experimental relevance of these findings. We finally show that the twist and bending energies of minicircles are governed by renormalized …
Resonant x-ray scattering shows that the bulk structure of the twist-bend liquid crystal phase, recently discovered in bent molecular dimers, has spatial periodicity without electron density modulation, indicating a lattice-free heliconical nematic precession of orientation that has helical glide symmetry. In situ study of the bulk helix texture for the dimer CB7CB shows an elastically-confined temperature-dependent minimum helix pitch, but a remarkable elastic softness of pitch in response to dilative stresses. Scattering from the helix is not detectable in the higher temperature nematic phas…
The structure of nematic liquid crystals formed by bent-core mesogens (BCMs) is studied in the context of Monte Carlo simulations of a simple molecular model that captures the symmetry, shape and flexibility of achiral BCMs. The results indicate the formation of (i) clusters exhibiting local smectic order, orthogonal or tilted, with strong in-layer polar correlations and anti-ferroelectric juxtaposition of successive layers and (ii) large homochiral domains through the helical arrangement of the tilted smectic clusters, whilst the orthogonal clusters produce achiral (untwisted) nematic states.
We provide a quantitative description of the helicoid--to--spiral transition in thin ribbons of nematic elastomers using an elementary calculation based on a Koiter-type plate with incompatible reference configuration. Our calculation confirms that such transition is ruled by the competition between stretching energy and bending energy.
Helical ribbons arise in many biological and engineered systems, often driven by anisotropic surface stress, residual strain, and geometric or elastic mismatch between layers of a laminated composite. A full mathematical analysis is developed to analytically predict the equilibrium deformed helical shape of an initially flat, straight ribbon, with prescribed magnitudes and orientations of the principal curvatures when subjected to arbitrary surface stress and/or internal residual strain distribution. The helix angle, radius, axis and chirality of the deformed helical ribbons are predicted with…
We study a minimal extension of the worm-like chain to describe polypeptides having alpha-helical secondary structure. In this model presence/absence of secondary structure enters as a scalar variable that controls the local chain bending modulus. Using this model we compute the extensional compliance of an alpha-helix under tensile stress, the bending compliance of the molecule under externally imposed torques, and the nonlinear interaction of such torques and forces on the molecule. We find that, due to coupling of the ``internal'' secondary structure variables to the conformational degrees …
