The nanostructure of two novel sulfur containing dimer materials has been investigated experimentally by hard and by resonant tender X-ray scattering techniques. On cooling the dimers through the nematic to twist-bend nematic (N-NTB) phase transition, the correlation length associated with short-range positional order drops, while the heliconical orientational order becomes more correlated. The heliconical pitch shows a stronger temperature dependence near the N-NTB transition than observed in previously studied dimers, such as the CBnCB series of compounds. We explain both this strong variation and the dependence of the heliconical pitch on the length of the spacer connecting the monomer units by taking into account a temperature dependent molecular bend and intermolecular overlap. and. The heliconical structure is observed even in the upper 3-4°C range of the smectic phase that forms just below the NTB state. The coexistence of smectic layering and the heliconical order indicates a SmCTB -type phase where the rigid units of the dimers are tilted with respect to the layer normal in order to accommodate the bent conformation of the dimers, but the tilt direction rotates along the heliconical axis. This is potentially similar to the SmCTB phase reported by Abberley et al (Nat. Commun. 2018, 9, 228) below a SmA phase.
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…
X-ray scattering and polarized microscopic studies of the structure and order parameters in the nematic (N) and heliconical, or the twist-bend nematic (Ntb), phase have been performed as a function of temperature. The nematic orientational order parameters <P2(cosθ)> and <P4(cosθ)> in the nematic phases of CB7CB and its mixtures with less than 20 wt% CB6CB reveal that they both increase with decreasing temperature in the N phase. Both order parameters decrease upon entering the Ntb phase and <P4(cosθ)> becomes negative providing a direct confirmation of the conical molecular orientational dist…
Helical structures are exciting and are utilized in numerous applications ranging from biotechnology to displays to medicine. Accurate description and understanding of resonance effects in helical structures provides crucial knowledge on molecular packing beyond positional ordering. We exam-ined the manifestation of resonance effects in a nematic phase with heliconical structure, the so called twist bend nematic (NTB) via tender resonant X-ray scattering (TReXS) at the sulfur K-edge. We demonstrate for the first time quantitatively that the energy dependence of the scattering peak in the NTB p…
Certain nematic liquid crystals, e.g., those formed by banana-shaped molecules, can exhibit a low-temperature twist-bend nematic (Ntb) phase. Upon addition of chiral dopants, a chiral version of the twist-bend phase (N*tb) can be observed below the conventional chiral nematic (N*) phase, while under electric field the N* phase is transformed into a specific state known as "heliconical cholesteric". In this work, we have studied the well-known Ntb-forming system CB7CB:CB6OCB with addition of 5CB and chiral dopants (ChD) using optical microscopy, differential scanning calorimetry (DSC), and meas…
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…
A series of asymmetric dimers with an odd number of atoms in the spacer were found to form different types of twisted structures despite being achiral. The formation of a variety of helical structures is accompanied by a gradual freezing of molecular rotation. The tight pitch heliconical nematic (NTB) phase and heliconical tilted smectic C (SmCTB) phase are formed. In the lowest temperature smectic phase, HexI, the twist is expressed through the formation of hierarchical structure: nano-scale helices and mesoscopic helical filaments. The short pitch helical structure in smectic phases is confi…
Unique electro-optical properties of the oblique helicoidal cholesteric (ChOH) stem from its heliconical director structure. An applied electric field preserves the single harmonic modulation of the director while tuning the ChOH period and the corresponding Bragg peak wavelength within a broad spectral range. We use the response of ChOH to the electric field to measure the elastic constants of twist K22 and bend K33 directly in the cholesteric phase. The temperature dependencies of K22 and K33 allow us to determine the range of the electric tunability of the ChOH pitch and the heliconical ang…
Heliconical cholesteric liquid crystals are expected to be more sensitive to torque induced by light field since their structure allows both bend and twist in molecular orientations, differently from the conventional cholesterics in which only twist deformation is involved, requiring much higher fields. We report here a demonstration of tuning the helical pitch in heliconical cholesterics induced by an optical torque. Experimental observations are in agreement with expectations of the classical theory extended to include the effect of the optical field. A dual control of the helical pitch is a…
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 …
Mesogenic dimers in the twist-bend nematic phase exhibit much higher flexoelectric polarization than in their uniform nematic phase. In order to theoretically investigate this data, we extend the symmetry based linear elastic theory of the twist-bend nematic phase developed in Phys. Rev. E 92, 030501(R) 2015, by including flexoelectricity under the action of an external electric field perpendicular to the helical axis. We show that at the nematic towards twist-bend nematic transition, a new flexoelectric mode becomes active. Consequently, the present model predicts the increase of the effectiv…
The nematic twist-bend ($\mathrm{N_{TB}}$) phase, exhibited by certain thermotropic liquid crystalline (LC) dimers, represents a new orientationally ordered mesophase -- the first distinct nematic variant discovered in many years. The $\mathrm{N_{TB}}$ phase is distinguished by a heliconical winding of the average molecular long axis (director) with a remarkably short (nanoscale) pitch and, in systems of achiral dimers, with an equal probability to form right- and left-handed domains. The $\mathrm{N_{TB}}$ structure thus provides another fascinating example of spontaneous chiral symmetry break…
We study dynamical optical response of a nematic liquid crystal cell that undergoes the splay-bend transition after applying the voltage across the cell. We formulate a simplified model that takes into account both the flexoelectric coupling and the surface rotational viscosity. The dynamic equations of the model were solved numerically to calculate temporal evolution of the director profile and the transmittance. We evaluate the response time as a function of a number of parameters characterising dielectric and elastic anisotropies, asymmetry of the surface pretilt angles, anchoring energy, s…
The extended Frank elastic energy density is used to investigate the existence of a stable periodically modulate structure that appears as a ground state exhibiting a twist-bend molecular arrangement. For an unbounded sample, we show that the twist-bend nematic phase $N_{TB}$ is characterized by a heliconical structure with a pitch in the nano-metric range, in agreement with experimental results. For a sample of finite thickness, we show that the wave vector of the stable periodic structure depends not only on the elastic parameters but also on the anchoring energy, easy axis direction, and th…
We analyze the interaction with uniform external fields of nematic liquid crystals within a recent generalized free-energy posited by Virga and falling in the class of quartic functionals in the spatial gradients of the nematic director. We review some known interesting solutions, i. e., uniform heliconical structures, which correspond to the so-called twist-bend nematic phase and we also study the transition between this phase and the standard uniform nematic one. Moreover, we find liquid crystal configurations, which closely resemble some novel, experimentally detected, structures called Sky…
The dielectric spectra of the twist bend nematic phase of the bent shaped achiral liquid crystal dimer are studied for the determination of the different relaxation modes. The two molecular processes were assigned one to the precessional rotation of the longitudinal components of the cyanobiphenyl groups and the second to the spinning rotation of the transverse component of the dimer. The low frequency peak shows a peculiar temperature behavior at the twist bend nematic to nematic transition. This peak can be assigned to a collective fluctuation of the tilt angle of the coarse grained director…
Using a novel Se-labelled dimer mixed with DTC5C7 aligned by magnetic field, the twist-bend nematic phase (Ntb) in dimers was studied by hard X-ray resonant scattering and by small and wide angle X-ray scattering (SAXS, WAXS). Resonant diffraction spots indicated a helix with a 9-12 nm pitch in the Ntb phase. Unprecedentedly high helix orien-tation enabled deconvolution of global and local order parameters. This, combined with simultaneous resonant and non-resonant SAXS and WAXS data, allowed us to construct a modified model of the Ntb phase matching twisted molecular conformations and the loc…
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.
While twist-bend nematic phases have been extensively studied, the experimental observation of two dimensional, oscillating splay-bend phases is recent. We consider two theoretical models that have been used to explain the formation of twist-bend phases -- flexoelectricity and bond orientational order -- as mechanisms to induce splay-bend phases. Flexoelectricity is a viable mechanism, and splay and bend flexoelectric couplings can lead to splay-bend phases with different modulations. We show that while bond orientational order circumvents the need for higher order terms in the free energy, th…
The critical behavior at the transition from uniform nematic to twist-bend modulated nematic phase is revealed and shown to be well explained by the mean field approximation. The study was performed on a group of materials that exhibit an unusually broad temperature range of the nematic phase above the twist-bend modulated nematic phase, so the critical range in which the order parameter fluctuations are strong and can be experimentally observed is wide. The formation of instantaneous helices is observed already several degrees above the transition temperature, strongly influencing the birefri…
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…
We describe the geometry of bend distortions in twist-bend nematic liquid crystals in terms of their fundamental degeneracies, which we call $β$ lines. These represent a new class of line-like topological defect. We use them to construct and characterise novel structures, including grain boundary and focal conic smectic-like defects, Skyrmions, and knotted merons. We analyse their local geometry and global structure, showing that their intersection with any surface is twice the Skyrmion number. Finally, we demonstrate how arbitrary knots and links can be created and describe them in terms of m…
Active materials are those in which individual, uncoordinated local stresses drive the material out of equilibrium on a global scale. Examples of such assemblies can be seen across scales from schools of fish to the cellular cytoskeleton and underpin many important biological processes. Synthetic experiments that recapitulate the essential features of such active systems have been the object of study for decades as their simple rules allow us to elucidate the physical underpinnings of collective motion. One system of particular interest has been active nematic liquid crystals (LCs). Because of…
The twist-bend nematic phase (NTB) is characterized by a conically twisting director and by a dramatic softening of the bend elastic constant before the transition to NTB phase. In the recently found splay nematic phase (NS) the splay elastic constant tends to zero, resulting in a splay modulation perpendicular to the director. We model both phases with a single Q-tensor free energy including a term that breaks the degeneracy between the splay and bend elastic constant, and a flexoelectric term coupling the divergence of the Q-tensor with polarization. NTB or NS phase is obtained by a change o…
Nematic twist--bend is the fifth nematic phase recognized in nature. This phase exhibits spiral orientational order, thus it is a chiral structure and it can be stabilized in systems composed of achiral molecules. The microscopic origin of this spontaneous chiral symmetry breaking is to a large extent unknown but phenomenologically it appears stabilized by assuming coupling between steric polar and orientational orderings. Understanding of how external fields affect the stability of this phase is of great intellectual interest and of relevance to potential applications. Within mesoscopic Landa…
We review the physics underlying Meyer's conjecture of how macroscopic-scale twist and bend conspire within the Frank-Oseen elasticity theory of nematics to create a heliconical arrangement of the uniaxial, apolar nematic director, the so-called "twist bend nematic" $\rm N_{TB}$. We show that since 2011 a second, lower-temperature nematic phase observed in odd methylene-linked cyanobiphenyl dimers discovered by Toriumi and called $\rm N_X$, has been incorrectly identified as $\rm N_{TB}$. Moreover, as more quantitative data on the $\rm N_X$ emerged, Meyer's simple prediction has been distorted…
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 …
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 …
A state of matter in which molecules show a long-range orientational order and no positional order is called a nematic liquid crystal. The best known and most widely used (for example, in modern displays) is the uniaxial nematic, with the rod-like molecules aligned along a single axis, called the director. When the molecules are chiral, the director twists in space, drawing a right-angle helicoid and remaining perpendicular to the helix axis; the structure is called a chiral nematic. In this work, using transmission electron and optical microscopy, we experimentally demonstrate a new nematic o…
We report a dynamic light scattering study of the fluctuation modes in a thermotropic liquid crystalline mixture of monomer and dimer compounds that exhibits the twist-bend nematic ($\mathrm{N_{TB}}$) phase. The results reveal a spectrum of overdamped fluctuations that includes two nonhydrodynamic and one hydrodynamic mode in the $\mathrm{N_{TB}}$ phase, and a single nonhydrodynamic plus two hydrodynamic modes (the usual nematic optic axis or director fluctuations) in the higher temperature, uniaxial nematic phase. The properties of these fluctuations and the conditions for their observation a…
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.
The twist-bend nematic phase, $N_{\rm TB}$, may be viewed as a heliconical molecular arrangement in which the director $\bf n$ precesses uniformly about an extra director field, $\bf t$. It corresponds to a nematic ground state exhibiting nanoscale periodic modulation. To demonstrate the stability of this phase from the elastic point of view, a natural extension of the Frank elastic energy density is proposed. The elastic energy density is built in terms of the elements of symmetry of the new phase in which intervene the components of these director fields together with the usual Cartesian ten…
Recently, Tavarone et al. (J. Chem. Phys. 143, 114505 (2015)) discussed phase behavior of zig-zag and bow-shaped particles composed of three needles. The authors presented very interesting results of extensive Monte Carlo simulations with periodic boundary conditions in the constant-NVT and the constant-NPT ensembles. In addition to isotropic, nematic, and smectic phases, they identified a modulated nematic, which is actually the nematic splay-bend phase ($N_{SB}$), long-anticipated for bent-core systems (Europhys. Lett. 56, 247 (2001)). They also described isotropic-nematic and nematic-smecti…
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…
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…
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…
Freeze Fracture Transmission Electron Microscopy (FFTEM) study of the nanoscale structure of the so-called "twist-bend" nematic (NX) phase of the cyanobiphenyl (CB) dimer molecule CB(CH2)7CB reveals a stripe texture of fluid layers periodically arrayed with a bulk spacing of d ~ 8.3 nm. Fluidity and a rigorously maintained spacing produce long-range-ordered fluid layered focal conic domains. Absence of a lamellar x-ray reflection at wavevector q ~ 2π/8 nm-1 or its harmonics in synchrotron-based scattering experiments indicates that this periodic structure is achieved with no detectable associa…
The nematic twist-bend (TB) phase, exhibited by certain achiral thermotropic liquid crystalline (LC) dimers, features a nanometer-scale, heliconical rotation of the average molecular long axis (director) with equally probable left- and right-handed domains. On meso to macroscopic scales, the TB phase may be considered as a stack of equivalent slabs or "pseudo-layers", each one helical pitch in thickness. The long wavelength fluctuation modes should then be analogous to those of a smectic-A phase, and in particular the hydrodynamic mode combining "layer" compression and bending ought to be char…
Confinement Reveals Hidden Splay-Bend Order in Twist-Bend Nematics
Institute of Theoretical Physics and Mark Kac Center for Complex Systems Research, Jagiellonian University（雅盖隆大学理论物理研究所与马克·卡克复杂系统研究中心）；International Institute for Sustainability with Knotted Chiral Meta Matter (WPI-SKCM²), Hiroshima University（广岛大学缠绕手性超物质可持续发展国际研究所）
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…
In this experimental and theoretical study, we examine the equilibrium shapes of quasitwo-dimensional twist-bend nematic (Ntb) drops formed within a planarly aligned nematic layer of the liquid crystal CB7CB. Initially, at the setting point of the Ntb phase, the drops assume a nonequilibrium cusped elliptical geometry with the major axis orthogonal to the director of the surrounding nematic fluid; this growth is governed principally by anisotropic heat diffusion. The drops attain equilibrium through thermally driven dynamical evolutions close to their melting temperature. They are associated w…
The nonlinear elastic properties of nematic liquid crystals have acquired new interest with the recent experimental observation of bulk modulated nematic phases which are composed by achiral molecules. We extend the Oseen-Zocher-Frank's elastic theory for nematic liquid crystals by including gradients of the nematic strain tensor in the elastic deformation energy. The invariants of the elastic tensor fields, up to the fourth order in the nematic director spatial derivatives, are calculated. An alternative approach that consists in the extension of the linear elastic energy to higher powers of …
We study the flow behaviour of a twist-bend nematic $(N_{TB})$ liquid crystal. It shows three distinct shear stress ($σ$) responses in a certain range of temperatures and shear rates ($\dotγ$). In Region-I, $σ\sim\sqrt{\dotγ}$, in region-II, the stress shows a plateau, characterised by a power law $σ\sim{\dotγ}^α$, where $α\sim0.1-0.4$ and in region-III, $σ\sim\dotγ$. With increasing shear rate, $σ$ changes continuously from region-I to II, whereas it changes discontinuously with a hysteresis from region-II to III. In the plateau (region-II), we observe a dynamic stress fluctuations, exhibitin…
We present magneto-optic measurements on two materials that form the recently discovered twist-bend nematic (Ntb) phase. This intriguing state of matter represents a new fluid phase that is orientationally anisotropic in three directions and also exhibits translational order with periodicity several times larger than the molecular size. NTB materials may also spontaneously form a visible, macroscopic stripe texture. We show that the optical stripe texture can be persistently inhibited by a magnetic field, and a 25T external magnetic field depresses the N-Ntb phase transition temperature by alm…
We report temperature dependencies of material properties such as dielectric anisotropy, birefringence, splay (K11), twist (K22), and bend (K33) elastic constants of the uniaxial nematic (N) phase formed by flexible dimers of DTC5C9 and compare their behavior to that of a corresponding monomer MCT5. DTC5C9 forms a twist-bend nematic (Ntb) at temperatures below the N phase. Anisotropic properties of MCT5 are typical of the rod-like mesogens. In particular, birefringence increases as the temperature is reduced, following the classic behavior, described by Haller. The elastic constants also follo…
Elasticity-Driven Periodic Polarization Patterns in Confined Chiral Ferroelectric Nematic Fluid
Jožef Stefan Institute（约瑟夫·斯特凡研究所）；Faculty of Mathematics and Physics, University of Ljubljana（卢布尔雅那大学数学与物理学院）；CENN Nanocenter（CENN纳米中心）；Department of Physics, Faculty of Science and Technology, University of the Basque Country UPV/EHU（巴斯克国立大学理学院物理系）；School of Chemistry, University of Leeds（利兹大学化学学院）；School of Physics and Astronomy, University of Leeds（利兹大学物理与天文学院）
In this work we present a simple qualitative model to describe shear rheological behavior of the twist-bend nematic liquid crystals. We find that at relatively low shear rate the effective viscosity decreases with the shear rate manifesting so-called shear-thinning phenomenon. At intermediate shear rate the stress is almost independent of the shear rate (a sort of plateau), and at large shear rate Newtonian rheology takes place. Within our theory we estimate the critical values of the shear rate in terms of coarse grained shear viscosity coefficients of the effective smectics equivalent to the…
We propose an extension of Frank-Oseen's elastic energy for bulk nematic liquid crystals which is based on the hypothesis that the fundamental deformations allowed in nematic liquid crystals are splay, twist and bend. The extended elastic energy is a fourth order form in the fundamental deformations. The existence of bulk spontaneous modulated or deformed nematic liquid crystal ground states is investigated. The analysis is limited to bulk nematic liquid crystals in the absence of limiting surfaces and/or external fields. The non deformed ground state is stable only when Frank-Oseen's elastic …
