Random (disordered) components in the surface anchoring of the smectic-A liquid crystalline film in general modify the thermal pseudo-Casimir interaction. Anchoring disorder of the quenched type is in general decoupled from the thermal pseudo-Casimir force and gives rise to an additional disorder-generated interaction, in distinction to the annealed disorder, whose effect on the pseudo-Casimir force is non-additive. We consider the effects of the surface anchoring disorder by assuming that one of the substrates of the film is contaminated by a disorder source, resulting in a Gaussian-weighted distribution of the preferred molecular anchoring orientation (easy axes) on that substrate, having a finite mean and variance or, more generally, a homogeneous in-plane, two-point correlation function. We show that the presence of disorder, either of the quenched or annealed type, leads to a significant reduction in the magnitude of the net thermal fluctuation force between the confining substrates of the film. In the quenched case this is a direct consequence of an additive free energy dependent on the variance of the disorder, while in the annealed case, the suppression of the interaction force can be understood based on a disorder-renormalized, effective anchoring strength.
Modeling and simulation studies using a high-order Landau-de Gennes type model for the direct isotropic/smectic-A liquid crystal transition are presented showing the existence of meta-stable nematic pre-ordering under certain conditions, in agreement with experimental observations (Tokita, M. et al. Macromolecules 2006, 39, 2021-2023)
Smectic blue phases (BPSm) are new mesophases of thermotropic liquid crystals, which exhibit a double geometrical frustration: the extension of chirality in three spatial dimensions like the classical blue phases, and helical twist competing with smectic order, as in the TGB phases. The existence of a quasi-long range smectic order in BPSm phases breaks the cubic symmetry of classical blue phases. The symmetries of these new phases have been determined by X-ray scattering and optical polarizing microscopy experiments.
We analyze the transverse intersubstrate pseudo-Casimir force, arising as a result of thermal fluctuations of the liquid crystalline layers of a smectic-A film confined between two planar substrates in a bookshelf geometry, in which the equidistant smectic layers are placed perpendicular to the bounding surfaces. We discuss the variation of the interaction force as a function of the intersubstrate separation in the presence of surface anchoring to the substrates, showing that the force induced by confined fluctuations is attractive and depends on the penetration length as well as the layer spa…
Extensions of a previously presented Landau-de Gennes type liquid crystalline phase transition model for the direct isotropic/smectic-A (lamellar) a phase transition to the direct isotropic/smectic-C (tilted lamellar) transition are studied. Two different proposed extensions to the model are studied both in the context of ideal ordering (point volume) and full three-dimensional uniaxial scalar/vector decomposition. Recommendations based upon the inclusion of essential physics and computational feasibility are made, distinguishing each of the two proposed extensions based upon these criteria. A…
An extension to a high-order model for the direct isotropic/smectic-A liquid crystalline phase transition was derived to take into account thermal effects including anisotropic thermal diffusion and latent heat of phase-ordering. Multi-scale multi-transport simulations of the non-isothermal model were compared to isothermal simulation, showing that the presented model extension corrects the standard Landau-de Gennes prediction from constant growth to diffusion-limited growth, under shallow quench/undercooling conditions. Non-isothermal simulations, where meta-stable nematic pre-ordering preced…
Institute of Nuclear Physics, Polish Academy of Sciences（波兰科学院核物理研究所）；Institute of Chemistry, Military University of Technology（军事科技大学化学研究所）；Faculty of Chemistry, Jagiellonian University（雅盖隆大学化学学院）；Research Center for Thermal and Entropic Science, Graduate School of Science, Osaka University（大阪大学理学研究科热力学与熵科学研究中心）
In this article we consider systems of parallel hard {\it superellipsoids}, which can be viewed as a possible interpolation between ellipsoids of revolution and cylinders. Superellipsoids are characterized by an aspect ratio and an exponent $α$ (shape parameter) which takes care of the geometry, with $α=1$ corresponding to ellipsoids of revolution, while $α=\infty$ is the limit of cylinders. It is well known that, while hard parallel cylinders exhibit nematic, smectic, and solid phases, hard parallel ellipsoids do not stabilize the smectic phase, the nematic phase transforming directly into a …
We have numerically studied a liquid composed of achiral, bent-shaped molecules built of tangent spheres. The system is known to spontaneously break mirror symmetry, as it forms a macroscopically chiral, twist-bend nematic phase [Phys. Rev. Lett. 115, 147801 (2015)]. Here, we have examined the full phase diagram of such liquid and observed several phases characterized by orientational and/or translational ordering of molecules. Apart from conventional nematic, smectic A, and the above-mentioned twist-bend nematic phase, we have identified antiferroelectric smectic A phase. For large densities …
Dispersions of rodlike colloidal particles exhibit a plethora of liquid crystalline states, including nematic, smectic A, smectic B, and columnar phases. This phase behavior can be explained by presuming the predominance of hard-core volume exclusion between the particles. We show here how the self-organization of rodlike colloids can be controlled by introducing a weak and highly localized directional attractive interaction between one of the ends of the particles. This has been performed by functionalizing the tips of filamentous viruses by means of regioselectively grafting fluorescent dyes…
Liquid crystalline systems exhibiting both macroscopic chirality and smectic order experience frustration resulting in mesophases possessing complex three-dimensional order. In the twist-grain-boundary phase, defect lattices mediate the propagation of twist throughout the system. We propose a new chiral smectic structure composed of a lattice of chiral bundles as a model of the helical nanofilament (B4) phase of bent core smectics.
High-resolution X-ray scattering studies of the nonpolar thermotropic liquid crystal 4-n-pentylphenylthiol-4'-n-octyloxybenzoate (\bar{8}S5) in aerosil gel nano-networks reveal that the aerosil-induced disorder significantly alters both the nematic to Smectic-A and Smectic-A to Smectic-C phase transitions. The limiting Smectic-A correlation length follows a power-law dependence on the aerosil density in quantitative agreement with the limiting lengths measured previously in other Smectic-A liquid crystal gels. The Smectic-A to Smectic-C liquid crystalline phase transition is altered fundamenta…
The 4,n-alkyloxybenzoic acid 6OBAC has a very rich variety of crystalline structures and two nematic sub-phases, characterised by different textures. It is a material belonging to a family of liquid crystals formed by hydrogen bonded molecules, the 4,n-alkyloxybenzoic acids indicates the homologue number). The homologues with n ranging from 7 to 13 display both smectic C and N phases. In spite of the absence of a smectic phase, 6OBAC exhibits two sub-phases with different textures, as it happens in other materials of the homologue series which possess the smectic phase. This is the first mater…
Computer simulation study of phase transitional behaviour of cholesterol molecules embedded with terminal dipole is reported. In this work, coarse-grained modeling of cholesteric molecules is done to study the influence of the coupled chiral and dipolar interactions on macroscopic liquid-crystalline phase formation. This NVT molecular dynamics simulation study demonstrates the formaton of novel Smectic Blue phase (BP\textsubscript{Sm}) which is a recent experimentally discovered chiral phase. Our study reveals that the higher strength of chiral interaction induces blue phase, whereas, larger d…
We investigate the self-organization of a binary mixture of similar sized rods and dipolar soft spheres by means of Monte-Carlo simulations. We model the interparticle interactions by employing anisotropic Gay-Berne, dipolar and soft-sphere interactions. In the limit of vanishing magnetic moments we obtain a variety of fully miscible liquid crystalline phases including nematic, smectic and lamellar phases. For the magnetic mixture, we find that the liquid crystalline matrix supports the formation of orientationally ordered ferromagnetic chains. Depending on the relative size of the species the…
We consider a nematic liquid crystal confined by two parallel planar interfaces, one being laterally homogeneous and the other provided by a substrate endowed with a periodic chemical stripe pattern. Based on continuum theory we analyze the influence of the lateral pattern on the liquid-crystalline Casimir force acting on the interfaces of the nematic cell at distance d due to the thermal fluctuations of the nematic director. For d much larger than the pattern periodicity, the influence of the patterned substrate can be described by a homogeneous, effective anchoring energy. By tuning this par…
We elucidate the roles of the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) transitions in magnetic field directed self-assembly of a liquid crystalline block copolymer (BCP), using \textit{in situ} x-ray scattering. Cooling into the nematic from the disordered melt yields poorly ordered and weakly aligned BCP microdomains. Continued cooling into the SmA however results in an abrupt increase in BCP orientational order with microdomain alignment tightly coupled to the translational order parameter of the smectic layers. These results underscore the significance of the N-SmA transition i…
Recent experiments on vesicles formed from block copolymers with liquid-crystalline side-chains reveal a rich variety of vesicle morphologies. The additional internal order ("structure") developed by these self-assembled block copolymer vesicles can lead to significantly deformed vesicles as a result of the delicate interplay between two-dimensional ordering and vesicle shape. The inevitable topological defects in structured vesicles of spherical topology also play an essential role in controlling the final vesicle morphology. Here we develop a minimal theoretical model for the morphology of t…
The McMillan liquid crystalline models under the influence of homeotropic anchoring walls and of external fields are investigated. For thin systems, the existence of the critical thickness, below which the system does not undergo a discrete phase transition, is confirmed. Apparent differences between the influence of the anchoring walls and of external fields are elucidated by investigating the order parameters and a temperature vs external field phase diagram for the bulk systems.
We propose a survey of those oxadiazole compounds, which are mesogenic. We will see that they can have bend-shaped molecules, a biaxial nematic phase, or other interesting peculiarities in the nematic and smectic phase. With large electric dipoles and luminescent properties, these materials are also very appealing for technological applications.
The dynamics of self-locomotion of active particles in aligned or liquid crystalline fluids strongly deviates from that in simple isotropic media. We explore the long-time dynamics of a swimmer moving in a three-dimensional smectic liquid crystal and find that the mean-square displacement (MSD) transverse to the director exhibits a distinct logarithmic tail at long times. The scaling is distinctly different from that in an isotropic or nematic fluid and hints at the subtle but important role of the director fluctuation spectrum in governing the long-time motility of active particles. Our findi…
We report a molecular dynamics simulation demonstrating that the Smectic B crystalline phase (Cr-B), commonly observed in mesogenic systems of anisotropic molecules, can be formed by a system of identical particles interacting via a spherically symmetric potential. The Cr-B phase forms as a result of a first order transition from an isotropic liquid phase upon isochoric cooling at appropriate number density. Its structure, determined by the design of the pair potential corresponds to Cr-B structure formed by elongated particles with the aspect ratio 1.8. The diffraction pattern, and the real-s…
We analyse the effect of thermal fluctuations on the elastic constants of the decoupled lamellar phase of tethered, crystalline membranes. Using a momentum-shell renormalization group technique, we show that the smectic-A -like compressional elastic constant, the in-plane Lamé coefficients, and the cross-coupling elastic constant vanish as (\ln q)^{- a} whereas the bend elastic constant diverges as (\ln q)^{b}, with a, b > 0, as the wavenumber q tends to zero. The exponents a and b satisfy the relation a + 3b = 2.
We demonstrate spontaneous wrinkling as a transient dynamical pattern in thin freely floating smectic liquid-crystalline films. The peculiarity of such films is that, while flowing liquid-like in the film plane, they cannot quickly expand in the direction perpendicular to that plane. At short time scales they therefore behave in two dimensions like quasi-incompressible membranes. Such films can develop a transient undulation instability or form bulges in response to lateral compression. Optical experiments with freely floating bubbles on parabolic flights and in ground lab experiments are repo…
Self-diffusion in isotropic and liquid crystalline phases of fd virus colloidal rods: a combined single particle tracking and differential dynamic microscopy study
For the first time we present analytical results for the contribution of electromagnetic fluctuations into thermodynamic properties of modulated systems, like cholesteric or smectic liquid crystalline films. In the case of small dielectric anisotropy we have derived explicit analytical expressions for the chemical potential of such systems. Two limiting cases were specifically considered: (i) the Van der Waals (VdW) limit, i.e., in the case when the retardation of the electromagnetic interactions can be neglected; and (ii) the Casimir limit, i.e. when the effects of retardation becomes conside…
Polymer vesicles are stable robust vesicles made from block copolymer amphiphiles. Recent progress in the chemical design of block copolymers opens up the exciting possibility of creating a wide variety of polymer vesicles with varying fine structure, functionality and geometry. Polymer vesicles not only constitute useful systems for drug delivery and micro/nano-reactors but also provide an invaluable arena for exploring the ordering of matter on curved surfaces embedded in three dimensions. By choosing suitable liquid-crystalline polymers for one of the copolymer components one can create ves…
The origin and structure of self assembled chiral liquid crystalline Blue Phase III (BPIII) have remained an enigma despite efforts spreading over decades. We report here an off-lattice NVT molecular dynamics simulation study of a system of polar chiral ellipsoidal molecules, which spontaneously exhibits BPIII , considering coarse-grained attractive-repulsive pair interaction appropriate for anisotropic liquid crystal mesogens. We have observed that suitable selection of chiral and dipolar strengths not only gives rise to thermodynamically stable BPIII but novel Smectic and Bilayered BPIII as …
The molecule 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene has gained a lot of attention, since high charge carrier mobility was observed in thin film transistors. Its thermotropic liquid crystalline states may play an important role in the thin film formation, since the smectic A and the smectic E phase (SmE) are claimed to be pre-stages of the final bulk structure. To understand the phase diversity, structural characterisation of solution processed thin films are performed by X-ray diffraction in the complete temperature range up to the isotropic state at 240°C. The diffraction patt…
We investigate the dynamic behavior of long guest rod-like particles immersed in liquid crystalline phases formed by shorter host rods, tracking both guest and host particles by fluorescence microscopy. Counter-intuitively, we evidence that long rods diffuse faster than short rods forming the one-dimensional ordered smectic-A phase. This results from the larger and non-commensurate size of the guest particles as compared to the wavelength of the energy landscape set by the lamellar stack of liquid slabs. The long guest particles are also shown to be still mobile in the crystalline smectic-B ph…
The orientational and translational order of a thermotropic ferroelectric liquid crystal (2MBOCBC) imbibed in self-organized, parallel, cylindrical pores with radii of 10, 15, or 20 nm in anodic aluminium oxide monoliths (AAO) are explored by high-resolution linear and circular optical birefringence as well as neutron diffraction texture analysis. The results are compared to experiments on the bulk system. The native oxidic pore walls do not provide a stable smectogen wall anchoring. By contrast, a polymeric wall grafting enforcing planar molecular anchoring results in a thermal-history indepe…
Computing stable configurations of confined smectic liquid crystals with a deep variational framework
School of Mathematical Sciences, Peking University（北京大学数学科学学院）；Columbia University（哥伦比亚大学）；Center for Applied Mathematics, Renmin University of China（中国人民大学应用数学中心）；School of Mathematical Sciences, Beijing International Center for Mathematical Research, Center for Quantitative Biology, Center for Machine Learning Research, Peking University（北京大学数学科学学院、北京国际数学研究中心、定量生物学中心、机器学习研究中心）
Based on simplifications of previous numerical calculations [Graf and Löwen, Phys. Rev. E \textbf{59}, 1932 (1999)], we propose algebraic free energy expressions for the smectic-A liquid crystal phase and the crystal phases of hard spherocylinders. Quantitative agreement with simulations is found for the resulting equations of state. The free energy expressions can be used to straightforwardly compute the full phase behavior for all aspect ratios and to provide a suitable benchmark for exploring how attractive interrod interactions mediate the phase stability through perturbation approaches su…
Experimental and modeling/simulation studies of phase equilibrium and growth morphologies of novel polymer-dispersed liquid crystal (PDLC) mixtures of PS (polystyrene) and liquid crystals that exhibit a direct isotropic/smectic-A (lamellar) mesophase transition were performed for PS/10CB (decyl- cyanobiphenyl) and PS/12CB (dodecyl-cyanobiphenyl). Partial phase diagrams were determined using polarized optical microscopy (POM) and differential scanning calorimetry (DSC) for different compositions of both materials, determining both phase separation (liquid/liquid demixing) and phase ordering (is…
Understanding the relaxation dynamics of colloidal suspensions is crucial to identify the elements that influence the mobility of their constituents, assess their macroscopic response across the relevant time and length scales, and thus disclose the fundamentals underpinning their exploitation in formulation engineering. In this work, we specifically assess the impact of long-ranged ordering on the relaxation dynamics of suspensions of soft-repulsive rod-like particles, which are able to self-organise into nematic and smectic liquid-crystalline phases. By performing Dynamic Monte Carlo simulat…
This paper reviews the research work on the liquid crystalline (LC) polymer vesicles (polymersomes), where the thermotropic nematic and smectic phases are displayed in the lyotropic bilayer polymer membrane. LC polymersomes possess the properties of both liquid crystals and polymers, the two essential soft matters. LC polymersomes offer, on the one hand, novel examples of the interplay between orientational order and the curved geometry of a two dimensional membrane. Spherical, ellipsoidal and tetrahedral vesicles are discussed. On the other hand, LC polymersomes enable novel design of stimuli…
We model a melt of monodisperse side-chain liquid crystalline polymers as a melt of comb copolymers in which the side groups are rod-coil diblock copolymers. We consider both excluded volume and Maier-Saupe interactions. The first acts among any pair of segments while the latter acts only between rods. Using a free energy functional calculated from this microscopic model, we study the spinodal stability of the isotropic phase against density and orientational fluctuations. The phase diagram obtained in this way predicts nematic and smectic instabilities as well as the existence of microphases …
A model of filaments of the TGBA phase arising from the homeotropic smectic A phase and nucleating on the sample surface is proposed. The model is based on the concept of finite blocks of parallel smectic layers forming a helical structure. The blocks are surrounded by dislocation loops. The model describes the filament structure near the sample surface and explains the observed inclination of the filament axis with respect to the easy direction of the molecular anchoring on the surface. The model is based on the observations of filament textures of the TGBA phase in a new chiral liquid crysta…
The wetting behavior of thin films of 4'-n-octyl-4-cyanobiphenyl (8CB) on Si is investigated via optical and x-ray reflectivity measurement. An experimental phase diagram is obtained showing a broad thick-thin coexistence region spanning the bulk isotropic-to-nematic ($T_{IN}$) and the nematic-to-smectic-A ($T_{NA}$) temperatures. For Si surfaces with coverages between 47 and $72\pm3$ nm, reentrant wetting behavior is observed twice as we increase the temperature, with separate coexistence behaviors near $T_{IN}$ and $T_{NA}$. For coverages less than 47 nm, however, the two coexistence behavio…
The phase-field-crystal model for liquid crystals is solved numerically in two spatial dimensions. This model is formulated with three position-dependent order parameters, namely the reduced translational density, the local nematic order parameter, and the mean local direction of the orientations. The equilibrium free-energy functional involves local powers of the order parameters up to fourth order, gradients of the order parameters up to fourth order, and different couplings between the order parameters. The stable phases of the equilibrium free-energy functional are calculated for various c…
Using the classical density functional theory of freezing and Monte Carlo computer simulations, we explore the liquid-crystalline phase behavior of hard rectangles on flat and cylindrical manifolds. Moreover, we study the effect of a static external field which couples to the rectangles' orientations, aligning them towards a preferred direction. In the flat and field-free case, the bulk phase diagram involves stable isotropic, nematic, tetratic, and smectic phases depending on the aspect ratio and number density of the particles. The external field shifts the transition lines significantly and…
Surface interactions can cause freely suspended thin liquid crystalline films to form phases different from the bulk material, but it is not known what happens at the surface of thick films. Edge dislocations can be used as a marker for the boundary between the bulk center and the reconstructed surface. We use noncontact mode atomic force microscopy to determine the depth of edge dislocations below the surface of freely suspended thick films of 4-n-heptyloxybenzylidene-4-n-heptylaniline (7O.7) in the crystalline B phase. 3.0 +/- 0.1 nm high steps are found with a width that varies with tempera…
We carry out Monte Carlo simulations to investigate the effect of molecular shape on liquid-crystal order. In our approach, each model mesogen consists of several soft spheres bonded rigidly together. The arrangement of the spheres may be straight (to represent uniaxial molecules), Z-shaped (for biaxial molecules), or banana-shaped (for bent-core molecules). Using this approach, we investigate the alignment of the nematic phase by substrates decorated with parallel ridges. We compare results for wide and narrow ridge spacing and examine local order near the substrates, and show that our result…
We report a novel multi-scale simulation methodology to quantitatively predict the thermodynamic behaviour of polymer mixtures, that exhibit phases with broken orientational symmetry. Our system consists of a binary mixture of oligomers and rod-like mesogens. Using coarse-grained molecular dynamics (CGMD) simulations we infer the topology of the temperature-dependent free energy landscape from the probability distributions of excess volume fraction of the components. The mixture exhibits nematic and smectic phases as a function of two temperature scales, the nematic-isotropic temperature $T_{N…
We report phase separation and liquid-crystal ordering induced by scalar activity in a system of Soft Repulsive Spherocylinders (SRS) of aspect ratio $L/D = 5 $. Activity was introduced by increasing the temperature of half of the SRS (labeled \textit{`hot'}) while maintaining the temperature of the other half constant at a lower value (labeled \textit{`cold'}). The difference between the two temperatures scaled by the lower temperature provides a measure of the activity. Starting from different equilibrium initial phases, we find that activity leads to segregation of the hot and cold particle…
We consider the effective pseudo-Casimir interaction forces mediated by a nematic liquid-crystalline film bounded by two planar surfaces, one of which imposes a random (disordered) distribution of the preferred anchoring axis in the so-called easy direction. We consider both the case of a quenched as well as an annealed disorder for the easy direction on the disordered surface and analyze the resultant fluctuation-induced interaction between the surfaces. In the case of quenched disorder, we show that the disorder effects appear additively in the total interaction and are dominant at intermedi…
The phase-field-crystal model is used to access the structure and thermodynamics of interfaces between two coexisting liquid crystalline phases in two spatial dimensions. Depending on the model parameters there is a variety of possible coexistences between two liquid crystalline phases including a plastic triangular crystal (PTC). Here, we calculate numerically the profiles for the mean density and the nematic order tensor across the interface for isotropic-PTC and columnar-PTC respectively smectic A-PTC coexistence. As a general finding, the width of the interface with respect to the nematic …
In this work we present results from NPT(isobaric-isothermal) Monte Carlo Simulation studies of Liquid Crystalline Dendrimer (LCDr) systems confined in a slit-pore made of two parallel flat walls. We investigate the substrate induced conformational and alignment properties of the system at different thermodynamic state points under uniform (unidirectional) anchoring condition. Tractable coarse grained force fields to model both monomer-monomer and monomer-substrate interaction potentials have been used from our previous work. In this anchoring condition, at lower pressure almost all the monome…
The pretransitional behavior of dodecylcyanobiphenyl (12CB) (isotropic-smectic-A-solid mesomorphism) with $d = 50$ nm $BaTiO_3$ nanoparticles (NPs) linked the cubic phase was monitored via temperature studies of dielectric constant. Tests were carried out in the isotropic, liquid crystal mesomorphic and solid phases. For each phase transition the same value of the critical exponent $α=0.5$ was obtained, including nanocolloids. All phase transitions show the weakly discontinuous nature. The temperature metric of the discontinuity dT notably decreases when adding nanoparticles. The addition of n…
