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Polarization flutter, produced by an applied AC electric field drives an equilibrium ferroelectric nematic ($\mathrm{N_F}$) liquid crystal (LC) through a transition into a dissipative active ferroelectric nematic state exhibiting strong elasto-hydrodynamic intermolecular interaction. In such a fluttering ferroelectric, the typical equilibrium $\mathrm{N_F}$ textural features adopted to reduce electrostatic energy, such as preferences for director bend, and alignment of polarization parallel to LC/air interfaces, are overcome, giving way to nonequilibrium conjugate structures in which director splay, and alignment of polarization normal to $\mathrm{N_F}$/air interfaces are preferred. Viewing the latter textures as those of an active nematic phase reveals that self-organization to reduce effective viscosity and resulting dissipation generates a flow-driven apparent nematic elasticity and interface structuring that dominates equilibrium LC elastic and surface forces., Comment: main paper (38 pages with 10 figures), supplement (6 pages)

We show that stable, freely suspended liquid crystal films can be made from the ferroelectric nematic ($\mathrm{N_F}$) phase and from the recently discovered polar, lamellar $\mathrm{SmZ_A}$ and $\mathrm{SmA_F}$ phases. The $\mathrm{N_F}$ films display two-dimensional, smectic-like parabolic focal conic textures comprising director/polarization bend that are a manifestation of the electrostatic suppression of director splay in the film plane. In the $\mathrm{SmZ_A}$ and $\mathrm{SmA_F}$ phases, the smectic layers orient preferentially normal to the film surfaces, a condition never found in typical thermotropic or lyotropic lamellar LC phases, with the $\mathrm{SmZ_A}$ films exhibiting focal-conic fan textures mimicking the appearance of typical smectics in glass cells when the layers are oriented normal to the plates, and the $\mathrm{SmA_F}$ films showing a texture of plaquettes of uniform in-plane orientation where both bend and splay are suppressed, separated by grain boundaries. The $\mathrm{SmA_F}$ phase can also be drawn into thin filaments, in which X-ray scattering reveals that the smectic layer planes are normal to the filament axis. Remarkably, the filaments are mechanically stable even if they break, forming free-standing, fluid filaments supported only at one end. The unique architectures of these films and filaments are stabilized by the electrostatic self-interaction of the liquid crystal polarization field, which enables the formation of confined, fluid structures that are fundamentally different from those of their counterparts made using previously known liquid crystal phases., Comment: Main paper 29 pages (5 figures); Supplement: 9 pages (9 figures)

We report the observation of a Twist Grain Boundary (TGB) phase of DNA, a striking motif of three dimensional (3D) equilibrium self-assembly of the DNA tetramer 5'-GTAC-3', a base sequence that is self-complimentary, pairing to form 4-base long, blunt-end Watson/Crick (WC) duplexes. Hydrophobic blunt ends and liquid crystal ordering enable these short duplexes to aggregate into long-DNA-like columns, even though the double helix has a break every 4 bases. A further step assembles these columns into monolayer sheets in which the columns are mutually parallel, and, finally, these sheets stack into lamellar arrays in which the column axis of each layer rotates in helical fashion, through a 60 degree angle with each passage to the next layer. This reorientation in a left-handed TGB helix enables each 2nm diameter WC column to be parallel to, and to partially enter, the major grooves of its neighbors., Comment: 21 pages, 3 figures

The idea that rod-like molecules possessing an electric dipole moment could exhibit a ferroelectric nematic phase was suggested more than a century ago. However, only recently such a phase has been reported for two quite different liquid crystals: RM734 (4-[(4-nitrophenoxy)carbonyl)]phenyl 2,4-dimethoxybenzoate) and DIO (2.3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2.6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate). For RM734 a direct ferroelectric nematic (NF) to classical nematic N transition was reported, whereas for DIO an intermediate phase Nx was discovered between the NF and the N phases. Here we present high-resolution calorimetric evidence that an intermediate Nx phase also exists in RM734 along a narrow temperature range between the NF and the N phases., Comment: 18 pages, 7 Figures

The collective behavior of the shortest DNA oligomers in high concentration aqueous solutions is an unexplored frontier of DNA science and technology. Here we broaden the realm of DNA nanoscience by demonstrating that single-component aqueous solutions of the DNA 4-base oligomer GCCG can spontaneously organize into three-dimensional (3D) periodic mesoscale frameworks. This oligomer can form B-type double helices by Watson-Crick (WC) pairing, into tiled brickwork-like duplex strands, which arrange into mutually parallel arrays and form the nematic and columnar liquid crystal phases, as is typical for long WC chains. However, at DNA concentrations above 400mg/mL, these solutions nucleate and grow an additional mesoscale framework phase, comprising a periodic network on a three dimensional body-centered cubic (BCC) lattice. This lattice is an array of nodes (valence-8, each formed by a pair of quadruplexes of GCCG terminal Gs), connected with a separation of 6.6 nm by struts (6-GCCG-long WC duplexes). This 3D-ordered DNA framework is of low density (DNA volume fraction ~0.2), but, due to its 3D crystal structure, is osmotically incompressible over its phase range. Atomistic simulations confirm the stability of such structures, which promise to form the basis of novel families of simply and inexpensively made nanoscale frameworks for templating and selection applications., Comment: 33 pages, 8 figures

The current intense study of ferroelectric nematic liquid crystals was initiated by the observation of the same ferroelectric nematic phase in two independently discovered organic rod-shaped mesogenic compounds, RM734 and DIO. We recently reported that the compound RM734 also exhibits a monotropic, low-temperature, antiferroelectric phase having reentrant isotropic symmetry (the $I_A$ phase), the formation of which is facilitated to a remarkable degree by doping with small (below $1\%$) amounts of the ionic liquid ${\rm BMIM-PF}_6$. Here we report similar phenomenology in DIO, showing that this reentrant isotropic behavior is not only a property of RM734 but is rather a more general, material-independent feature of ferroelectric nematic mesogens. We find that the reentrant isotropic phases observed in RM734 and DIO are similar but not identical, adding two new phases to the ferroelectric nematic realm. The two $I_A$ phases exhibit similar, strongly peaked, diffuse x-ray scattering in the WAXS range $(1

We report a transition from the ferroelectric nematic liquid crystal ($N_F$) phase to a lower-temperature, antiferroelectric fluid phase having reentrant isotropic symmetry ($I_A$), in the liquid crystal compound RM734 doped with small concentrations of the ionic liquids BMIM or EMIM. Even a trace amount of ionic liquid dopant facilitates the kinetic pathway for the transition from the $N_F$ to the $I_A$, enabling simple cooling to produce this isotropic fluid phase rather than resulting in crystallization. The $I_A$ was also obtained in the absence of specific ionic liquid doping by appropriate temperature cycling in three distinct, as-synthesized-and-purified batches of RM734, two commercial and one from our laboratory. An additional birefringent, lamellar-modulated, antiferroelectric phase with the director parallel to the layers, resembling the smectic $Z_A$, is found between the paraelectric and ferroelectric nematic phases in RM734/BMIM mixtures., Comment: 45 pages, including Supplementary Information

Mechanically quenching a thin film of smectic-C liquid crystal results in the formation of a dense array of thousands of topological defects in the director field. The subsequent rapid coarsening of the film texture by the mutual annihilation of defects of opposite sign has been captured using high-speed, polarized light video microscopy. The temporal evolution of the texture has been characterized using an object-detection convolutional neural network to determine the defect locations, and a binary classification network customized to evaluate the brush orientation dynamics around the defects in order to determine their topological signs. At early times following the quench, inherent limits on the spatial resolution result in undercounting of the defects and deviations from expected behavior. At intermediate to late times, the observed annihilation dynamics scale in agreement with theoretical predictions and simulations of the $2$D XY model., Comment: 11 pages, 10 figures

Polymorphism, the phenomenon that a species can exist in many discrete forms, is common in nature, such as hair colors in an animal species, flower colors in a tree species, and blood types in humans, etc. In materials science, it refers to a solid that can exist in multiple forms with different crystalline structures. In the liquid crystals field, however, polymorphism is hard to find because a discontinuous structural variation is basically impossible because of their fluid or partially fluid nature. Herein we show that the B4 and DC phases that for many years have been classified as distinctive phases are connected, in terms of their nano-architectures, based on the study of a single compound, a flexible bent-shaped dimer. The surrounding solvent is the key to assisting the dimeric molecules in morphing and adopting different supramolecular structures at the mesoscale. Furthermore, we accidentally find a novel nanotube-like structure that has not yet been reported in view of the B4/DC phases. Together with the known sponge (DC) and the helical filament (B4) structures, they are just some of the manifestations of the polymorphism in a class of low-birefringence, chiral phase from achiral liquid crystals., Comment: M: 16p, 5f; SI: 9p, 9f

The combination of large spontaneous polarization and fluidity makes the newly discovered ferroelectric nematic liquid crystalline phase (NF) responsive to electric fields in ways that have no counterpart in other materials. We probe this sensitive field response by confining a NF fluid in microchannels that connect electrodes through straight and curved paths. We find that by applying electric fields as low as E c.a. 0.5 V/mm, the NF phase orders with its polarization smoothly following the winding paths of the channels even when oriented antiparallel to the line connecting positive to negative electrodes, implying analogous behavior of the electric field. Upon inversion of E, the polar order undergoes a complex multistage switching process dominated by electrostatic interactions. Multistage polarization switching dynamics is also found in numerical simulations of a quasi-2D continuum model of NF liquid crystals in microchannels, which also clarify the conditions under which the electric field is guided by the microchannels. Experiments and theory indicate that all observations are direct consequences of the prompt effective screening of electric field components normal to the channel walls. This electric "superscreening" effect emerges as a distinctive property of the NF phase, capable of inducing conditions in which both the polarization and the electric field are guided by microchannels., Comment: Paper Submitted

Numerous measurements of the dielectric constant $\epsilon$ of the recently discovered ferroelectric nematic ($N_F$) liquid crystal (LC) phase report extraordinarily large values of $\epsilon^\prime$ (up to ~30,000). We show that what is in fact being measured in such experiments is the high capacitance of the non-ferroelectric, interfacial, insulating layers of nanoscale thickness that bound the $N_F$ material in typical cells. We analyze a parallel-plate cell filled with $N_F$ material of high-polarization $\mathbf{P}$, oriented parallel to the plates at zero applied voltage. Minimization of the dominant electrostatic energy renders $\mathbf{P}$ spatially uniform and orients it to make the electric field in the $N_F$ as small as possible, a condition under which the voltage applied to the cell appears almost entirely across the high-capacity interfacial layers. This coupling of orientation and charge creates a combined polarization-external capacitance (PCG) Goldstone reorientation mode requiring applied voltages orders of magnitude smaller than that of the $N_F$ layer alone to effectively transport charge across the $N_F$ layer. The $N_F$ layer acts as a low-value resistor and the interfacial capacitors as reversible energy storage reservoirs, lowering the restoring force (mass) of the PCG mode and producing strong reactive dielectric behavior. Analysis of data from several experiments on ferroelectric liquid crystals (chiral smectics C, bent-core smectics, and the $N_F$ phase supports the PCG model, showing that deriving dielectric constants from electrical impedance measurements of high-polarization ferroelectric LCs, without properly accounting for the self-screening effects of polarization charge and the capacitive contributions of interfacial layers, can result in overestimation of the $\epsilon^\prime$ values of the LC by many orders of magnitude., Comment: 30 pages of text, 11 figures, 59 references (47 pages total)

We report the smectic $A_F$, a new liquid crystal phase of the ferroelectric nematic realm. The smectic $A_F$ is a phase of small polar, rod-shaped molecules which 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 $\sim 10$ Debye longitudinal molecular dipoles, and hysteretic polarization reversal with a coercive field of about $2 \times 10^5$ V/m is observed. The smectic $A_F$ phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic ($N$) -- smectic $Z_A$ (Sm$Z_A$) -- ferroelectric nematic ($N_F$) -- smectic $A_F$ (Sm$A_F$) phase sequence; and 7N/DIO, exhibiting an $N$ -- Sm$Z_A$ -- Sm$A_F$ phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers., Comment: 26 pages, 6 figures

We investigated the electrostatic behavior of ferroelectric liquid droplets exposed to the pyroelectric field of a lithium niobate ferroelectric crystal substrate. The ferroelectric liquid is a nematic liquid crystal in which almost complete polar ordering of the molecular dipoles generates an internal macroscopic polarization locally collinear to the mean molecular long axis. Upon entering the ferroelectric phase by reducing the temperature from the nematic phase, the liquid crystal droplets become electromechanically unstable and disintegrate by the explosive emission of fluid jets. These jets are mostly interfacial, spreading out on the substrate surface, and exhibit fractal branching out into smaller streams to eventually disrupt, forming secondary droplets. We understand this behavior as a manifestation of the Rayleigh instability of electrically charged fluid droplets, expected when the electrostatic repulsion exceeds the surface tension of the fluid. In this case the charges are due to the bulk polarization of the ferroelectric fluid which couples to the pyroelectric polarization of the underlying lithium niobate substrate through its fringing field and solid-fluid interface coupling. Since the ejection of fluid does not neutralize the droplet surfaces, they can undergo multiple explosive events as the temperature decreases., Comment: 15 pages, 10 figures

We have structurally characterized the liquid crystal phase that appears 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-year-old void in the taxonomy of smectics 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. The period of this polarization wave ($\sim$180 A) is mesoscopic, corresponding to $\sim$40 molecules side-by-side, indicating that this lamellar structure is collectively stabilized. A Landau free energy, originally formulated to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-Sm$Z_A$-ferroelectric nematic phase sequence., Comment: main paper (with 7 figures) and supplement (with 12 figures) comprise 65 pages

The organic mesogens RM734 and DIO are members of separate molecular families featuring distinct molecular structures. These families, at the present time, are the only ones known to exhibit a ferroelectric nematic liquid crystal (LC) phase. Here we present an experimental investigation of the phase diagram and electro-optics of binary mixtures of RM734 and DIO. We observe paraelectric nematic (N) and ferroelectric nematic (NF) phases in both materials, each of which exhibits complete miscibility across the phase diagram, showing that the paraelectric and ferroelectric are the same phases in RM734 as in DIO. Remarkably, these molecules form ideal mixtures with respect to both the paraelectric-ferroelectric nematic phase behavior and the ferroelectric polarization density of the mixtures, the principal order parameter of the transition. Ideal mixing is also manifested in the orientational viscosity, and the onset of glassy dynamics at low temperature. This behavior is attributable in part to the similarity of their overall molecular shape and net longitudinal dipole moment (~ 11 Debye), and to a common tendency for head-to-tail molecular association. In contrast, the significant difference in molecular structures leads to poor solubility in the crystal phases, enhancing the stability of the ferroelectric nematic phase at low temperature in the mixtures and making possible room temperature electro-optic effects. In the mixtures with excess DIO, an intermediate phase appears via an ultraweak, first-order transition from the N phase, in a narrow temperature range between the paraelectric and ferroelectric nematics., Comment: main paper has 24 pages with 5 figures; supplementary information has 14 pages with 8 figures

Machine learning techniques have been developed to identify inclusions on the surface of freely suspended smectic liquid crystal films imaged by reflected light microscopy. The experimental images are preprocessed using Canny edge detection and then passed to a radial kernel support vector machine (SVM) trained to recognize circular islands and droplets. The SVM is able to identify these objects of interest with an accuracy that far exceeds that of conventional tracking software, especially when the background image is non-uniform or when the target features are in close proximity to one another. This method could be applied to tracking objects in a variety of visually inhomogeneous biological and soft matter environments, in order to study growth dynamics, the development of spatial order, and hydrodynamic behavio, Comment: 13 pages,1 figures, 1 table

We show that surface interactions can vectorially structure the three-dimensional polariza-tion 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 mac-roscopic 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 {\pi}-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 twist-ed 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 anti-parallel-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 wP ~ 3x10-3 J/m2., Comment: 34 pages, including 5 figures and bibliography

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 microcoulombs/cm-sqd, the largest ever measured for an organic material or for any fluid. 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 long axes in the nematic. We find a host of spectacular optical and hydrodynamic effects driven by ultra-low applied field (E~1V/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 science and technology based on the enhanced understanding, development, and exploitation of molecular electrostatic interaction., Comment: main paper: 23 pages; SI 34 pages

We demonstrate a method for training a convolutional neural network with simulated images for usage on real-world experimental data. Modern machine learning methods require large, robust training data sets to generate accurate predictions. Generating these large training sets requires a significant up-front time investment that is often impractical for small-scale applications. Here we demonstrate a `full-stack' computational solution, where the training data set is generated on-the-fly using a noise injection process to produce simulated data characteristic of the experimental system., Comment: 10 pages, 8 figures

Two dimensional (2D) laminar jet-----a stream of fluid that projected into a surrounding medium with the flow confined in 2D-----has both theoretical and experimental significance. We carried out 2D laminar jet experiments in freely suspended liquid crystal films (FSLCFs) of nanometers thick and centimeters in size, in which individual molecules are confined to single layers thus enable film flows with two degrees of freedom. The experimental observations are found in good agreement with the classic 2D laminar jet theory of ideal cases that assume no external coupling effects, even in fact there exist strong coupling force from the ambient air. We further investigated this air coupling effect in computer simulations, with the results indicated air has little influence on the velocity maps of flow near the nozzle. This astonishing results could be intuitively understood by considering 2D incompressibility of the films. This experiment, together with a series of our previous experiments, show for a wide range of Reynolds number, FSLCFs are excellent testing beds for 2D hydrodynamics., Comment: 6 pages, 8 figures

Experimental and theoretical studies of a smectic-hexatic transition in freely suspended films of 54COOBC compound are presented. X-ray investigations revealed a discontinuous first-order transition into the hexatic phase. Moreover, the temperature region of two phase coexistence near the phase transition point diminishes with film thickness. The coexistence width dependence on film thickness was derived on the basis of the Landau mean-field theory in the vicinity of the tricritical point (TCP). Close to TCP the surface hexatic ordering penetrates anomalously deep into the film interior., Comment: 19 pages, 7 figures, 49 references

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 {\AA} on heating, the trimer exhibits an essentially temperature-independent pitch of 66 {\AA}, significantly shorter than those reported for other twist-bend forming materials in the literature. We attribute this to a specific combination of intrinsic conformational bend of the trimer molecules and a sterically favorable intercalation of the trimers over a commensurate fraction (two-thirds) of the molecular length. We develop a geometric model of the twist-bend phase for these materials with the molecules arranging into helical chain structures, and we fully determine their respective geometric parameters., Comment: supplemental information included

Freely suspended films of smectic liquid crystals are unique examples of quasi two-dimensional fluids. Mechanically stable and with quantized thickness of the order of only a few molecular layers, smectic films are ideal systems for studying fundamental fluid physics, such as collective molecular ordering, defect and fluctuation phenomena, hydrodynamics, and nonequilibrium behavior in two dimensions (2D), including serving as models of complex biological membranes. Smectic films can be drawn across openings in planar supports resulting in thin, meniscus-bounded membranes, and can also be prepared as bubbles, either supported on an inflation tube or floating freely. The quantized layering renders smectic films uniquely useful in 2D fluid physics. The OASIS team has pursued a variety of ground-based and microgravity applications of thin liquid crystal films to fluid structure and hydrodynamic problems in 2D and quasi-2D systems. Parabolic flights and sounding rocket experiments were carried out in order to explore the shape evolution of free floating smectic bubbles, and to probe Marangoni effects in flat films. The dynamics of emulsions of smectic islands (thicker regions on thin background films) and of microdroplet inclusions in spherical films, as well as thermocapillary effects, were studied over extended periods within the OASIS (Observation and Analysis of Smectic Islands in Space) project on the International Space Station. We summarize the technical details of the OASIS hardware and give preliminary examples of key observations.

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 2{\pi}Rmol, where Rmol is the radius of bend curvature of a single all-trans CB7CB molecule. This relation emerges from a model which simply relates the macroscopic characteristics of the helical structure, which is mostly biaxial twist and has little bend, to the bent molecular shape. This connection comes about through the presence in the fluid of self-assembled oligomer-like correlations of interlocking molecules, arising from the nanosegregation of rigid and flexible molecular subcomponents, forming a brickwork tiling of pairs of molecular strands into a duplex double-helical chain., Comment: Supplementary Information included

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 phase., Comment: Supplemental Materials included

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 birefringence. We confirm the presence of nanoscale modulations of the molecular orientation in the mixtures by freeze-fracture transmission electron microscopy (FFTEM), further evidence of their twist-bend nature. We devise and implement a statistical approach to quantitatively measure the ground state pitch of the twist-bend phase and its mixtures using FFTEM. The addition of 5CB generally shifts the measured ground-state pitch distributions towards larger pitch. Interestingly, the pitch appears to increase discontinuously by ~10 nm at the 50 wt% concentration of 5CB, indicating that the twist-bend phase undergoes a structural transition at higher 5CB concentrations., Comment: Supplementary information included

Using atomistic molecular dynamics simulation we study the discotic columnar liquid crystalline (LC) phases formed by a new organic compound having Hexa-peri-Hexabenzocoronene (HBC) core with six pendant oligothiophene units recently synthesized by Nan Hu et al. (N. Hu, R. Shao, Y. Shen, D. Chen, N. A. Clark and D. M. Walba, Adv. Mater. 26, 2066, 2014). This HBC core based LC phase was shown to have electric field responsive behavior and has important application in organic electronics. Our simulation results confirm the hexagonal arrangement of columnar LC phase with a lattice spacing consistent with that obtained from small angle X-ray diffraction data. We have also calculated various positional and orientational correlation functions to characterize the ordering of the molecules in the columnar arrangement. The molecules in a column are arranged with an average twist of 25 degrees having an average inter-molecular separation of ~5 {\AA}. Interestingly, we find an overall tilt angle of 43 degrees between the columnar axis and HBC core. We also simulate the charge transport through this columnar phase and report the numerical value of charge carrier mobility for this liquid crystal phase. The charge carrier mobility is strongly influenced by the twist angle and average spacing of the molecules in the column.

Ferrofluids are familiar as colloidal suspensions of ferromagnetic nanoparticles in aqueous or organic solvents. The dispersed particles are randomly oriented but their moments become aligned if a magnetic field is applied, producing a variety of exotic and useful magneto-mechanical effects. A longstanding interest and challenge has been to make such suspensions macroscopically ferromagnetic, that is having uniform magnetic alignment in absence of a field. Here we report a fluid suspension of magnetic nanoplates which spontaneously aligns into an equilibrium nematic liquid crystal phase that is also macroscopically ferromagnetic. Its zero-field magnetization produces distinctive magnetic self-interaction effects, including liquid crystal textures of fluid block domains arranged in closed flux loops, and makes this phase highly sensitive, with it dramatically changing shape even in the Earth's magnetic field.

The Brownian diffusion of micron-scale inclusions in freely suspended smectic A liquid crystal films a few nanometers thick and several millimeters in diameter depends strongly on the air surrounding the film. Near atmospheric pressure, the three-dimensionally coupled film/gas system is well described by Hughes/Pailthorpe/White hydrodynamic theory but at lower pressure (p < 70 torr), the diffusion coefficient increases substantially, tending in high vacuum toward the two-dimensional limit where it is determined by film size. In the absence of air, the films are found to be a nearly ideal physical realization of a two-dimensional, incompressible Newtonian fluid., Comment: 5 pages, 3 figures

We study experimentally and theoretically the hydrodynamic interaction of pairs of circular inclusions in two-dimensional, fluid smectic membranes suspended in air. By analyzing their Brownian motion, we find that the radial mutual mobilities of identical inclusions are independent of their size but that the angular coupling becomes strongly size-dependent when their radius exceeds a characteristic hydrodynamic length. The observed dependence of the mutual mobilities on inclusion size is described well for arbitrary separations by a model that generalizes the Levine/MacKintosh theory of point-force response functions and uses a boundary-element approach to calculate the mobility matrix.

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- and right-handed domains in a chiral conglomerate., Comment: 19 pages, 4 figures

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 ~ 2{\pi}/8 nm-1 or its harmonics in synchrotron-based scattering experiments indicates that this periodic structure is achieved with no detectable associated modulation of the electron density, and thus has nematic molecular ordering. A search for periodic ordering with d ~ 8nm in CB(CH2)7CB using atomistic molecular dynamic computer simulation yielded equilibration of a conical twist-bend helixed nematic ground state, of the sort first proposed by Meyer, and envisioned in systems of bent molecules by Dozov and Memmer, We identify {\theta} ~ 33 degree as the cone angle, and p ~ 8nm as the full pitch of the helix, the shortest ever found in a nematic fluid., Comment: 21 pages, 6 figures

We present a study of a water-in-oil microemulsion in which surfactant coated water nanodroplets are dispersed in the isotropic phase of the thermotropic liquid crystal 5CB. As the temperature is lowered below the isotropic to nematic phase transition of pure 5CB, the system displays a demixing transition leading to a coexistence of a droplet rich isotropic phase with a droplet poor nematic. The transition is anticipated, in the high T side, by increasing pretransitional fluctuations in 5CB molecular orientation and in the nanodroplet concentration. The observed phase behavior supports the notion that the nanosized droplets, while large enough for their statistical behavior to be probed via light scattering, are also small enough to act as impurities, disturbing the local orientational ordering of the liquid crystal and thus experiencing pretransitional attractive interaction mediated by paranematic fluctuations. The pretransitional behavior, together with the topology of the phase diagram, can be understood on the basis of a diluted Lebwohl-Lasher model which describes the nanodroplets simply as holes in the liquid crystal., Comment: 64 pages, 16 figures, J. Chem. Phys. in press

Our previous molecular dynamic simulation studies of simple two-dimensional (2D) systems \cite{matt_big} suggested that both geometrical defects (localized, large-amplitude deviations from hexagonal ordering) and topological defects (dislocations and disclinations) play a role in 2D melting. To capture the main features of the 2D melting transition and investigate the respective roles of these two classes of defects, we study a discrete elastic model consisting of an array of nodes connected by springs, for which the relative number of geometrical defects (modeled as broken springs) and topological defects (nodes having a coordination number different from 6) may be precisely controlled. We preform Monte Carlo simulations of this model in the isobaric-isothermal ensemble, and present the phase diagram as well as various thermodynamic, statistical and structural quantities as a function of the relative populations of geometrical and topological defects. The model exhibits a rich phase behavior including hexagonal and square crystals, expanded crystal, dodecagonal quasicrystal, and liquid structure. We found that the solid--liquid transition temperature is lowered by a factor 3 to 4, with respect to the case when only topological defects are allowed, when both topological and geometrical defects are permitted, supporting our hypothesis concerning the central role played by the geometrical defects in the melting. The microscopic structure of the dense liquid has been investigated and the results are compared to those from simulations of 2D particle systems., Comment: 20 pages Revtex, 9 jpeg figures

We have carried out Monte Carlo simulations of zig-zag shaped molecules where the the molecules is composed of three rigidly linked hard spherocylinder arranged in a zigzag fashion. By varying zigzag angle we have mapped out the whole phase diagram as a function of pressure, molecular density and zigzag angle $\Psi$. For $\Psi$ between $35^0$ and $80^0$ our model simulation exhibits SmC phase. This is the first conclusive evidence where steric interaction arising out of molecular shape alone induce the occurrence of SmC phase for a wide range of zigzag angle. For smaller $\Psi$, a transition from tilted crystal (XT) to nontlted crystal is observed., Comment: 4 pages Revtex, 4 eps figures

We point out that the phenomenon ``heating by freezing'' discovered in nonequilibrium simulations by Helbing, et al. (PRL 84, 1240 (2000)) extends to equilibrium systems as well. We argue that such reentrant fluctuation-driven freezing can, for example, be realized in two-dimensional colloidal systems subjected to a one-dimensional periodic potential., Comment: 4 RevTeX pgs

Recently, a new class of smectic liquid crystal phases (SmCP phases) characterized by the spontaneous formation of macroscopic chiral domains from achiral bent-core molecules has been discovered. We have carried out Monte Carlo simulations of a minimal hard spherocylinder dimer model to investigate the role of excluded volume interations in determining the phase behavior of bent-core materials and to probe the molecular origins of polar and chiral symmetry breaking. We present the phase diagram as a function of pressure or density and dimer opening angle $\psi$. With decreasing $\psi$, a transition from a nonpolar to a polar smectic phase is observed near $\psi = 167^{\circ}$, and the nematic phase becomes thermodynamically unstable for $\psi < 135^{\circ}$. No chiral smectic or biaxial nematic phases were found., Comment: 4 pages Revtex, 3 eps figures (included)

Recent experiments indicate that doping low concentrations of bent-core molecules into calamitic smectic solvents can induce anticlinic and biaxial smectic phases. We have carried out Monte Carlo (MC) simulations of mixtures of rodlike molecules (hard spherocylinders with length/breadth ratio $L_{\rm rod}/D = 5$) and bow- or banana-shaped molecules (hard spherocylinder dimers with length/breadth ratio $L_{ban}/D = 5$ or 2.5 and opening angle $\psi$) to probe the molecular-scale organization and phase behavior of rod/banana mixtures. We find that a low concentration (3%) of $L_{ban}/D = 5$ dimers induces anticlinic (SmC$_A$) ordering in an untilted smectic (SmA) phase for $100^\circ \le \psi < 150^\circ$. For smaller $\psi$, half of each bow-shaped molecule is nanophase segregated between smectic layers, and the smectic layers are untilted. For $L_{ban}/D = 2.5$, no tilted phases are induced. However, with decreasing $\psi$ we observe a sharp transition from {\sl intralamellar} nanophase segregation (bow-shaped molecules segregated within smectic layers) to {\sl interlamellar} nanophase segregation (bow-shaped molecules concentrated between smectic layers) near $\psi = 130^\circ$. These results demonstrate that purely entropic effects can lead to surprisingly complex behavior in rod/banana mixtures., Comment: 5 pages Revtex, 7 postscript figures

We have developed a class of idealized models of chromonic molecules which are miscible in water, but which can form aggregates which in turn organize into lyotropic liquid crystal (LC) phases. By carrying out Monte Carlo simulation in a binary mixture of model chromonic and water molecules, we have studied the effect of concentration and molecular shape on the nature of resulting mesophases. We have also computed the free energy associated with the formation of chromonic columnar aggregates by umbrella sampling. Our free energy computation helps us to verify the isodesmic behavior which is characteristic of chromonic systems. For isodesmic behavior the addition of each chromonic molecule to the columnar aggregates is accompanied by a constant free energy increment and the net free energy decreases with increasing column length., Comment: 27 pages Revtex, 15 postscript figures (4 color figures). High resolution color figures available upon request