The understanding of self-organization in the twist-bend nematic $(N_\text{TB})$ phase, identified in 2011 in liquid crystal dimers, is at the forefront of soft matter research worldwide. This new nematic phase develops structural chirality in the isotropic $(I)$ and the uniaxial nematic $(N_\text{U})$ phases, despite the fact that the molecules forming the structure are chemically achiral. Molecular, shape-induced flexopolarization provides a viable mechanism for a qualitative understanding of $N_\text{TB}$ and the related phase transitions. The key question that remains is whether with this mechanism one can also explain quantitatively the presently existing experimental data. To address this issue we propose a generalization of the mesoscopic Landau-de Gennes theory of nematics, where higher-order elastic terms of the alignment tensor are taken into account, in addition to the lowest-order flexopolarization coupling. The theory is not only capable of explaining the appearance of $N_\text{TB}$ but also stays in quantitative agreement with experimental data. In exemplary calculations, we take the data known for CB7CB flexible dimer - the "drosophila fly" in the studies of $N_\text{TB}$ [A. Jákli et al., Rev. Mod. Phys. 90, 045004 (2018)] - and estimate the constitutive parameters of the model from temperature variation of the nematic order parameter and the Frank elastic constants in the nematic phase. Then we seek for relative stability and properties of the isotropic, uniaxial nematic and twist-bend nematic phases. In particular, we evaluate various properties of $N_\text{TB}$, like temperature variation of the structure's wave vector, conical angle, flexopolarization, and remaining order parameters. We also look into the fine structure of $N_\text{TB}$, like its biaxiality - the property, which is difficult to access experimentally at the nanoscale.
Using Landau-de Gennes effective theory for nematic liquid crystals we analyse the structure of rectilinear n=1/2 smooth disclination line in the case of equal elastic constants. We find that at certain temperature there is an exact mathematical correspondence with a rectilinear vortex in superfluid $^4He$. With a help of polynomial approximation difference of free energies of the smooth and of a singular disclination lines is estimated. It turns out that the smooth disclination line is energetically preferred only if temperature is low enough. At higher temperatures a disordered core should b…
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…
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 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 …
We investigate stability properties of the radially symmetric solution corresponding to the vortex defect (so called "melting hedgehog") in the framework of the Landau - de Gennes model of nematic liquid crystals. We prove local stability of the melting hedgehog under arbitrary $Q$-tensor valued perturbations in the temperature regime near the critical supercooling temperature. As a consequence of our method, we also rediscover the loss of stability of the vortex defect in the deep nematic regime.
We propose an efficient numerical scheme, based on the method of lines, for solving the Landau-de Gennes equations describing the relaxational dynamics of nematic liquid crystals. Our method is computationally easy to implement, balancing requirements of efficiency and accuracy. We benchmark our method through the study of the following problems: the isotropic-nematic interface, growth of nematic droplets in the isotropic phase and the kinetics of coarsening following a quench into the nematic phase. Our results, obtained through solutions of the full coarse-grained equations of motion with no…
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…
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…
In the Landau-de Gennes theory on nematic liquid crystals, the well-known Landau-de Gennes energy depends on four elastic constants; $L_1$, $L_2$, $L_3$, $L_4$. For the general case of $L_4\neq 0$, Ball-Majumdar \cite {BM} found an example that the Landau-de Gennes energy functional from physics literature \cite{MN} does not satisfy a coercivity condition, which causes a problem in mathematics to establish existence of energy minimizers. In order to solve this problem, we observe that the original third order term on $L_4$, proposed by Schiele and Trimper \cite{ST} in physics, is a linear comb…
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 elastomers do not show the discontinuous, first-order, phase transition that the Landau-De Gennes mean field theory predicts for a quadrupolar ordering in 3D. We attribute this behavior to the presence of network crosslinks, which act as sources of quenched orientational disorder. We show that the addition of weak random anisotropy results in a singular renormalization of the Landau-De Gennes expression, adding an energy term proportional to the inverse quartic power of order parameter Q. This reduces the first-order discontinuity in Q. For sufficiently high disorder strength the jump …
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…
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 …
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…
Numerical modeling of nematic liquid crystals using the tensorial Landau-de Gennes (LdG) theory provides detailed insights into the structure and energetics of the enormous variety of possible topological defect configurations that may arise when the liquid crystal is in contact with colloidal inclusions or structured boundaries. However, these methods can be computationally expensive, making it challenging to predict (meta)stable configurations involving several colloidal particles, and they are often restricted to system sizes well below the experimental scale. Here we present an open-source…
In our previous work,, we studied asymptotic behavior of minimizers of the Landau-de Gennes energy functional on planar domains as the nematic correlation length converges to zero. Here we improve upon those results, in particular by sharpening the description of the limiting map of the minimizers. We also provide an expression for the energy valid for a small, but fixed value of the nematic correlation length.
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…
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…
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…
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…
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…
We demonstrate that a first order isotropic-to-nematic phase transition in liquid crystals can be succesfully modeled within the generalized Landau-de Gennes theory by selecting an appropriate combination of elastic constants. The numerical simulations of the model established in this paper qualitatively reproduce the experimentally observed configurations that include interfaces and topological defects in the nematic phase.
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…
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 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…
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…
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…
Within the framework of the generalized Landau-de Gennes theory, we identify a $Q$-tensor-based energy that reduces to the four-constant Oseen-Frank energy when it is considered over orientable uniaxial nematic states. Although the commonly considered version of the Landau-de Gennes theory has an elastic contribution that is at most cubic in components of the $Q$-tensor and their derivatives, the alternative offered here is quartic in these variables. One clear advantage of our approach over the cubic theory is that the associated minimization problem is well-posed for a significantly wider ch…
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 …
We propose a Landau-de Gennes phenomenological model to describe the pressure induced smectic A-nematic phase transition. The pressure induced smectic A phase transitions are discussed for varying coupling between orientational and translational order parameter. Increasing the pressure, the first order nematic-smectic A transition becomes second order at a tricritical point which agrees fairly with available experimental results.
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…
Defects in liquid crystals are of great practical importance and theoretical interest. Despite tremendous efforts, predicting the location and transition of defects under various topological constraint and external field remains to be a challenge. We investigate defect patterns of nematic liquid crystals confined in three-dimensional spherical droplet and two-dimensional disk under different boundary conditions, within the Landau-de Gennes model. We implement a spectral method that numerically solves the Landau-de Gennes model with high accuracy, which allows us to study the detailed static st…
We revisit the classic problem of the structure of the isotropic-nematic interface within Ginzburg-Landau-de Gennes theory, refining previous analytic treatments of biaxiality at the interface. We compare our analysis with numerical results obtained through a highly accurate spectral collocation scheme for the solution of the Landau-Ginzburg-de Gennes equations. In comparison to earlier work, we obtain improved agreement with numerics for both the uniaxial and biaxial profiles, accurate asymptotic results for the decay of biaxial order on both nematic and isotropic sides of the interface and a…
We construct a phenomenological Landau-de Gennes theory for hard colloidal rods by performing an order parameter expansion of the chemical-potential dependent grand potential. By fitting the coefficients to known results of Onsager theory, we are not only able to describe the isotropic-nematic phase transition as function of density, including the well-known density jump, but also the isotropic-nematic planar interface. The resulting theory is applied in calculations of the isotropic core size in a radial hedgehog defect, the density dependence of linear defects of hard rods in square confinem…
We present a numerical method, based on a tensor order parameter description of a nematic phase, that allows fully anisotropic elasticity. Our method thus extends the Landau-de Gennes $\mathbf{Q}$-tensor theory to anisotropic phases. A microscopic model of the nematogen is introduced (the Maier-Saupe potential in the case discussed in this paper), combined with a constraint on eigenvalue bounds of $\mathbf{Q}$. This ensures a physically valid order parameter $\mathbf{Q}$ (i.e., the eigenvalue bounds are maintained), while allowing for more general gradient energy densities that can include cub…
We present numerical and analytic results for uniaxial and biaxial order at the isotropic-nematic interface within Ginzburg-Landau-de Gennes theory. We study the case where an oblique anchoring condition is imposed asymptotically on the nematic side of the interface, reproducing results of previous work when this condition reduces to planar or homoeotropic anchoring. We construct physically motivated and computationally flexible variational profiles for uniaxial and biaxial order, comparing our variational results to numerical results obtained from a minimization of the Ginzburg-Landau-de Genn…
Uniaxial nematic liquid crystals whose molecular orientation is subjected to a tangential anchoring on a curved surface offer a non trivial interplay between the geometry and the topology of the surface and the orientational degree of freedom. We consider a general thin film limit of a Landau-de Gennes Q-tensor model which retains the characteristics of the 3D model. From this, previously proposed surface models follow as special cases. We compare fundamental properties, such as alignment of the orientational degrees of freedom with principle curvature lines, order parameter symmetry and phase…
Several attractive properties of hydrocarbon-linked mesogenic dimers have been discovered, a major feature of these has been the ability of dimers under confinement to form periodic patterns. At least six different types of stripe-like periodic patterns can be observed in these materials under various experimental conditions. Our most recent finding is the discovery of micrometre-scale periodic patterns at the N-Ntb phase transition interface, and sub-micrometre scale patterns in the Ntb phase. Layer-like sub-micrometre patterns were observed using three-photon excitation fluorescence polarizi…
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…
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…
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 respons…
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…
Infrared spectroscopy (IR) and quantum chemistry calculations, based on density functional theory (DFT) were used to study the structure and the molecular interactions in the nematic (N) and twist-bend (NTB) phases of thioether-linked dimers. Infrared absorbance measurements were conducted in a polarized beam for homogeneously aligned samples to measure and understand the orientation of the vibrational transition dipole moments in the liquid crystal states. Revealing temperature-dependent changes in the mean IR absorbance in the twist-bend nematic phase were observed. In the transition from th…
