Translational Order Research Articles

3D Tomographic Analysis of the Order-Disorder Interplay in the Pachyrhynchus congestus mirabilis Weevil.

The bright colors of Pachyrhynchus weevils originate from complex dielectric nanostructures within their elytral scales. In contrast to previous work exhibiting highly ordered single‐network diamond‐type photonic crystals, here, it is shown by combining optical microscopy and spectroscopy measurements with 3D focused ion beam (FIB) tomography that the blue scales of P. congestus mirabilis differ from that of an ordered diamond structure. Through the use of FIB tomography on elytral scales filled with platinum (Pt) by electron beam‐assisted deposition, it is revealed that the red scales of this weevil possess a periodic diamond structure, while the network morphology of the blue scales exhibit diamond morphology only on the single scattering unit level with disorder on longer length scales. Full wave simulations performed on the reconstructed volumes indicate that this local order is sufficient to open a partial photonic bandgap even at low dielectric constant contrast between chitin and air in the absence of long‐range or translational order. The observation of disordered and ordered photonic crystals within a single organism opens up interesting questions on the cellular origin of coloration and studies on bio‐inspired replication of angle‐independent colors.

Slave-master mechanism of thermotropic liquid crystal phase transitional behavior

We introduce the slave-master mechanism in the phase behavior of two-component systems where both components could exhibit some kind of (quasi) long-range order. The key feature of the mechanism is that one component strongly influences the other while the reverse influence is negligible. To illustrate the effect, we consider systems where each isolated component exhibits an order-disorder phase transition on varying a control parameter (e.g., temperature) to which we refer as the generalized temperature. We present a minimal model that shows robust slave-master behavior. As exemplary systems, we present thermotropic liquid crystals (LCs) exhibiting nematic and smectic A phase order, focusing on the interaction strength between orientational and translational order. Mixtures of nematic LC molecules and anisotropic nanoparticles are also presented. We show that qualitatively different behaviors could emerge via the specific nature of the inter-component interaction. Mastering this mechanism could lead to various applications based on phase tunable properties.

Impact of random-field-type disorder on nematic liquid crystalline structures.

We study bicomponent systems where one component represents a liquid crystalline (LC) phase, and the other component randomly perturbs the LC order. Such systems can serve as a testbed to systematically analyse the impact of qualitatively different types of random-type sources of perturbation on the orientational and/or translational order. This mini-review presents typical representatives of such systems, where orientational and translational order is probed in nematic and smectic A LCs, respectively. As a source of perturbation, we consider either different porous matrices (control-pore glass, aerogels) or aerosil nanoparticles, which can form in LCs' different fractal-like network organizations. In such complex systems, LC ordering fingerprints the interplay among LC elastic forces, interfacial forces, and randomness. The resulting LC behaviour could be characterised by either long-range, quasi long-range, or short-range order. We demonstrate under which conditions random-field-like phenomena or interfacial effects dominate. However, these effects are relatively strongly entangled in most experimental systems, andindividual impacts cannot be precisely identified.

Experimental evidence of tetrahedral symmetry breaking in SiO2 glass under pressure

Bimodal behavior in the translational order of silicon’s second shell in SiO2 liquid at high temperatures and high pressures has been recognized in theoretical studies, and the fraction of the S state with high tetrahedrality is considered as structural origin of the anomalous properties. However, it has not been well identified in experiment. Here we show experimental evidence of a bimodal behavior in the translational order of silicon’s second shell in SiO2 glass under pressure. SiO2 glass shows tetrahedral symmetry structure with separation between the first and second shells of silicon at low pressures, which corresponds to the S state structure reported in SiO2 liquid. On the other hand, at high pressures, the silicon’s second shell collapses onto the first shell, and more silicon atoms locate in the first shell. These observations indicate breaking of local tetrahedral symmetry in SiO2 glass under pressure, as well as SiO2 liquid.

How Far Is "Bulk Water" from Interfaces? Depends on the Nature of the Surface and What We Measure.

Using systematic molecular dynamics (MD) simulations, we revisit the question: At what distance from an interface do the properties of "bulk water" get recovered? We have considered three different kinds of interfaces: nonpolar (hydrophobic; isooctane-water interface), charged (negative; AOT bilayer), and polar (zwitterionic; POPC bilayer). In order to interrogate the extent of perturbation of the interfacial water molecules as a function of the distance from the interface, we utilize a diverse range of structural and dynamical parameters. To capture the structural perturbations, we look into local density (translational order), local tetrahedral order parameter, and dipolar orientation of the water molecules. We also explore the anisotropic diffusion of the water molecules in the direction perpendicular to the interface as well as the planar diffusion parallel to the interface in a distance dependent manner. In addition, the orientational time correlation functions have been computed to understand the extent of slowdown in the rotational dynamics. As expected, the electrostatic field emanating from the charged AOT interface seems to have the highest long-range effect on the orientational order and dynamics of the water molecules, whereas specific interactions like hydrogen bonding and electrostatic interaction lead to significant trapping and kinetic slowdown for both AOT and POPC (zwitterionic) very close to the interface. Our analysis highlights that not only the length-scale of perturbation depends on the nature of the interfaces and specific interactions but also the type of water property that we measure/calculate. Different water properties seem to have widely different length-scale of perturbation. Orientational order parameters seem to be perturbed to a much longer length-scale as compared to translational order parameters. The global orientational order of water can be perturbed even up to ∼4-5 nm near the negatively charged AOT surface in the absence of any extra electrolyte. This observation has significant implication toward the interpretation of experimental measurements as well since different spectroscopic techniques would probe different parameters or water properties with possible mutual disagreement and inconsistency between different types of measurements. Thus, our study provides a broader and unifying perspective toward the aspect of "context dependent" structural and dynamical perturbation of "interfacial water".

Long-time relaxation dynamics in nematic and smectic liquid crystals of soft repulsive colloidal rods.

Understanding the relaxation dynamics of colloidal suspensions is crucial to identifying the elements that influence the mobility of their constituents, assessing their macroscopic response across the relevant time and length scales, and thus disclosing 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 rodlike particles, which are able to self-organize into nematic and smectic liquid-crystalline phases. Rods are modeled as soft repulsive spherocylinders with a length-to-diameter ratio L^{★}=5, interacting via the truncated and shifted Kihara potential. By performing dynamic Monte Carlo simulations, we analyze the effect of translational and orientational order on the diffusion of the rods along the relevant directions imposed by the morphology of the background phases. To provide a clear picture of the resulting dynamics, we assess its dependence on temperature, which can dramatically determine the response time of the system relaxation and the self-diffusion coefficients of the rods. The computation of the van Hove correlation functions allows us to identify the existence of rods that diffuse significantly faster than the average and whose concentration can be accurately adjusted by a suitable choice of temperature.

Aroyloxycinnamates with wide mesophase temperature ranges

ABSTRACT A new series of eight asymmetric homologues was designed and synthesised by the reaction of aroyloxybenzaldehydes with Wittig salt of methyl bromoacetate, where the length of the alkoxy chain was varied. All the compounds were found thermally stable up to 220°C. Differential scanning calorimetry, polarising optical microscopy and X-ray diffraction were used to study the mesomorphic properties, where a mesophase range of up to 80°C was obtained. The two shorter homologues with C3–C4 were nematic, the intermediate lengths were nematic and smectic A (SmA) with a progressive increase of the SmA domains and the longest homologue with C12 was purely SmA. The translational order parameter of the SmA mesophases showed that the molecular order inside the smectic layers increases with molecular length, associated with the higher stabilisation and predominance of the SmA phase. All compounds dispersed in solution absorb light in the ultraviolet region.

Trade-offs between Translational and Orientational Order in 2D Superlattices of Polygonal Nanocrystals with Differing Edge Count.

The goal of this work is to identify factors which modulate structural order in 2D self-assembled superlattices of polygon-shaped colloidal nanocrystals. Using combined experimental and simulation techniques, we quantify order in superlattices of hexagonal prism-shaped CdSe/CdS nanocrystals and cube-shaped CsPbBr3 nanocrystals. Superlattices derived from cube-shaped nanocrystals display less translational order compared to hexagonal prism-shaped nanocrystals both experimentally and in simulations. This effect can be attributed to geometric considerations inherent to the combined rotational and translational symmetries of different polygonal shapes and their superlattices. Cubes form a simple cubic lattice where nanocrystals can slide without steric overlap, whereas hexagonal prisms interlock, preventing translation. Regarding orientational order, cube assemblies display a narrower orientation distribution. Intuitively, hexagonal prisms are a more "spherical" shape compared to cubes. The results presented here outline a conceptual framework for identifying superlattice structures which favor translationally and orientationally ordered self-assembled superlattices.

Topographic Control of Order in Quasi-2D Granular Phase Transitions.

We experimentally investigate the nature of 2D phase transitions in a quasi-2D granular fluid. Using a surface decorated with periodically spaced dimples we observe interfacial tension between coexisting granular liquid and crystal phases. Measurements of the orientational and translational order parameters and associated susceptibilities indicate that the surface topography alters the order of the phase transition from a two-step continuous one to a first-order liquid-solid one. The interplay of boundary inelasticity and geometry, either order promoting or inhibiting, controls whether it is the granular crystal or the granular fluid which makes contact with the edge. This order induced wetting has important consequences, determining how coexisting phases separate spatially.

Metallic glasses and metallic glass nanostructures for functional electrocatalytic applications

This brief review reports the recent advancement of metallic glasses and metallic glass nanostructures for functional electrocatalytic applications. Metallic glasses (MGs) or amorphous metals result from quenching the melts at a high cooling rate (e.g., 106 K/s), bypassing crystallization. Metallic glasses are devoid of long-range translational order, no defects like grain boundaries, and multiple elements included. Due to these unique structural features, MG′s show distinct and valuable mechanical, physical and chemical properties and therefore were widely studied as a structural material for decades. Even though MGs were proposed for catalytic applications earlier, a comprehensive study or attempt to apply these materials successfully in electrocatalytic applications are few since the intrinsic surface area is comparably lesser. A rejuvenated interest among the research community for applying various novel strategies in catalytic applications of MGs is highlighted in the present review. Theoretical approaches using density functional theory (DFT) and high-throughput screening assisted with machine learning paradigm advances the discovery of new MGs, which demonstrated high potential for catalytic applications. We focus on the basic features and recent advances in the MGs for catalytic applications like electrocatalytic water splitting reactions like HER, OER, fuel cell reactions like ORR, alcohol oxidation reactions like MOR, EOR, and degradation of harmful organic dyes from the industrial effluents. The presently advancing strategies for enhancing the performance of these metallic glass electrocatalysts through nanostructuring and high-throughput screening are discussed. The unique atomic-scale structural mechanism of the metallic glasses, which can favor the development of high-performance electrocatalysts even comparable to currently available precious-metal-based catalysts, will be discussed. Finally, we also give future directions on designing novel and superior metallic glass-based advanced catalysts.

Alignment destabilizes crystal order in active systems.

We combine numerical and analytical methods to study two-dimensional active crystals formed by permanently linked swimmers and with two distinct alignment interactions. The system admits a stationary phase with quasi-long-range translational order, as well as a moving phase with quasi-long-range active force director and velocity order. The translational order in the moving phase is significantly influenced by alignment interaction. For Vicsek-like alignment, the translational order is short ranged, whereas the bond-orientational order is quasi-long ranged, implying a moving hexatic phase. For elasticity-based alignment, the translational order is quasi-long ranged parallel to the motion and short ranged in the perpendicular direction, whereas the bond orientational order is long ranged. We also generalize these results to higher dimensions.

Defining Swelling Kinetics in Block Copolymer Thin Films: The Critical Role of Temperature and Vapour Pressure Ramp.

We studied the kinetics of swelling in high-χ lamellar-forming poly(styrene)-block- poly(lactic acid) (PS-b-PLA) block copolymer (BCP) by varying the heating rate and monitoring the solvent vapour pressure and the substrate temperature in situ during solvo-thermal vapour annealing (STVA) in an oven, and analysing the resulting morphology. Our results demonstrate that there is not only a solvent vapour pressure threshold (120 kPa), but also that the rate of reaching this pressure threshold has a significant effect on the microphase separation and the resulting morphologies. To study the heating rate effect, identical films were annealed in a tetrahydrofuran (THF) vapour environment under three different ramp regimes, low ), medium and high , for 60, 90 and 120 min, respectively, while the solvent vapour pressure and the substrate temperature were measured in real time. The translational order improved significantly with increasing the heating rate. The solvent mass uptake calculated for the different ramp regimes during annealing is linearly proportional to time, indicating that the swelling kinetics followed Case II diffusion. Two stages of the swelling behaviour were observed: (i) diffusion at the initial stages of swelling and (ii) stress relaxation, controlled at later stages. Films with a faster rate of increase in vapour pressure ) reached the pressure threshold value at an early stage of the swelling and attained a good phase separation. According to our results, highly ordered patterns are only obtained when the volume fraction of the solvent exceeds the polymer volume fraction, i.e., , during the swelling process, and below this threshold value , the films did not obtain a good structural order, even at longer annealing times.

Phase behavior of rotationally asymmetric Brownian kites containing 90° internal angles* *Project supported by the National Natural Science Foundation of China (Grant Nos. 11874277 and 21621004, and 11704276) and the Natural Science Foundation of Tianjin, China (Grant No. 19JCQNJC14900).

Previous Monte Carlo simulations have shown that ordered tetratic phases can emerge in a dense two-dimensional Brownian system of rotationally asymmetric hard kites having 90° internal angles. However, there have been no experimental investigations yet to compare with these simulation results. Here, we have fabricated two types of micron-sized kites having internal angles of 72°–90°–108°–90° and 72°–99°–90°–99°, respectively, and we have experimentally studied their phase behavior in two-dimensional systems. Interestingly and in contrast to the Monte Carlo simulations, the experimental results show a phase sequence of isotropic fluid-hexagonal rotator crystal-square crystal as the area fraction ϕ A increases for both types of kites. The observed square crystal displays not only a quasi-long-range translational order but also (quasi-)long-range 4-fold bond- and molecular-orientational order; these characteristics confirm that tetratic order can emerge even in dense Brownian systems of rotationally asymmetric particles. A model based on local polymorphic configurations (LPCs) is proposed to understand the origin of the square lattice order in these dense kite systems. The results in this study provide a new route to realize custom-designed self-assembly of colloids by controlling LPCs.

Material Science for catalysis: Quo vadis?

Material Science for catalysis: Quo vadis?

Liquid-Crystal Ordering and Microphase Separation in the Lamellar Phase of Rod-Coil-Rod Triblock Copolymers. Molecular Theory and Computer Simulations.

A molecular model of the orientationally ordered lamellar phase exhibited by asymmetric rod-coil-rod triblock copolymers has been developed using the density-functional approach and generalizing the molecular-statistical theory of rod-coil diblock copolymers. An approximate expression for the free energy of the lamellar phase has been obtained in terms of the direct correlation functions of the system, the Flory-Huggins parameter and the Maier-Saupe orientational interaction potential between rods. A detailed derivation of several rod-rod and rod-coil density-density correlation functions required to evaluate the free energy is presented. The orientational and translational order parameters of rod and coil segments depending on the temperature and triblock asymmetry have been calculated numerically by direct minimization of the free energy. Different structure and ordering of the lamellar phase at high and low values of the triblock asymmetry is revealed and analyzed in detail. Asymmetric rod-coil-rod triblock copolymers have been simulated using the method of dissipative particle dynamics in the broad range of the Flory-Huggins parameter and for several values of the triblock asymmetry. It has been found that the lamellar phase appears to be the most stable one at strong segregation. The density distribution of the coil segments and the segments of the two different rods have been determined for different values of the segregation strength. The simulations confirm the existence of a weakly ordered lamellar phase predicted by the density-functional theory, in which the short rods separate from the long ones and are characterized by weak positional ordering.

Different Mechanisms of Translational Symmetry Breaking in Liquid-Crystal Coil–Rod–Coil Triblock Copolymers

A molecular-statistical theory of coil-rod–coil triblock copolymers with orientationally ordered rod-like fragments has been developed using the density functional approach. An explicit expression for the free energy has been obtained in terms of the direct correlation functions of the reference disordered phase, the Flory–Huggins parameter and the potential of anisotropic interaction between rigid rods. The theory has been used to derive several phase diagrams and to calculate numerically orientational and translational order parameter profiles for different polymer architecture as a function of the Flory–Huggins parameter, which specifies the short-range repulsion and as functions of temperature. In triblock copolymers, the nematic–lamellar transition is accompanied by the translational symmetry breaking, which can be caused by two different microscopic mechanisms. The first mechanism resembles a low dimensional crystallization and is typical for conventional smectic liquid crystals. The second mechanism is related to the repulsion between rod and coil segments and is typical for block copolymers. Both mechanisms are analyzed in detail as well as the effects of temperature, coil fraction and the triblock asymmetry on the transition into the lamellar phase.

Observation of a topological defect lattice in the charge density wave of 1T-TaS2

Charge density wave (CDW) phases native to the transition metal dichalcogenide 1T-TaS2 are probed through a graphene layer covering its surface by using local scanning tunneling microscopy/spectroscopy and transport measurements. We show that over a wide range of temperatures, the graphene cover, while protecting the air-sensitive 1T-TaS2 from oxidation, does not obstruct access to the electronic properties of the CDW. At room temperature, where the system is in the nearly commensurate CDW phase, we observe contiguous domains of the CDW phase separated by a network of topological defects. These topological defects, dubbed CDW vortices, form a lattice with a quasi-long range translational order, which resembles the Bragg glass phase in Abrikosov vortex lattices in type-II superconductors. While the quasi-long range order in the CDW itself is not uncommon, its existence in the CDW vortex lattice is observed here for the first time. Finally, when reducing the temperature to 78 K into the commensurate CDW phase, we find that the graphene cover layer acquires properties consistent with a proximity-induced CDW.

Vanishing nematic order beyond the pseudogap phase in overdoped cuprate superconductors

During the last decade, translational and rotational symmetry-breaking phases-density wave order and electronic nematicity-have been established as generic and distinct features of many correlated electron systems, including pnictide and cuprate superconductors. However, in cuprates, the relationship between these electronic symmetry-breaking phases and the enigmatic pseudogap phase remains unclear. Here, we employ resonant X-ray scattering in a cuprate high-temperature superconductor [Formula: see text] (Nd-LSCO) to navigate the cuprate phase diagram, probing the relationship between electronic nematicity of the Cu 3d orbitals, charge order, and the pseudogap phase as a function of doping. We find evidence for a considerable decrease in electronic nematicity beyond the pseudogap phase, either by raising the temperature through the pseudogap onset temperature T* or increasing doping through the pseudogap critical point, p*. These results establish a clear link between electronic nematicity, the pseudogap, and its associated quantum criticality in overdoped cuprates. Our findings anticipate that electronic nematicity may play a larger role in understanding the cuprate phase diagram than previously recognized, possibly having a crucial role in the phenomenology of the pseudogap phase.

Dodecagonal quasicrystals of oil-swollen ionic surfactant micelles

A delicate balance of noncovalent interactions directs the hierarchical self-assembly of molecular amphiphiles into spherical micelles that pack into three-dimensional periodic arrays, which mimic intermetallic crystals. Herein, we report the discovery that adding water to a mixture of an ionic surfactant and n-decane induces aperiodic ordering of oil-swollen spherical micelles into previously unrecognized, aqueous lyotropic dodecagonal quasicrystals (DDQCs), which exhibit local 12-fold rotational symmetry and no long-range translational order. The emergence of these DDQCs at the nexus of dynamically arrested micellar glasses and a periodic Frank-Kasper (FK) σ phase approximant sensitively depends on the mixing order of molecular constituents in the assembly process and on sample thermal history. Addition of n-decane to mixtures of surfactant and water instead leads only to periodic FK A15 and σ approximants with no evidence for aperiodic order, while extended ambient temperature annealing of the DDQC also reveals its transformation into a σ phase. Thus, these lyotropic DDQCs are long-lived metastable morphologies, which nucleate and grow from a stochastic distribution of micelle sizes formed by abrupt segregation of varied amounts of oil into surfactant micelles on hydration. These findings indicate that molecular building block complexity is not a prerequisite for the formation of aperiodic supramolecular order, while also establishing the generic nature of quasicrystalline states across metal alloys and self-assembled micellar materials.

Reverse order-disorder transition of Janus particles confined in two dimensions.

Janus particles with different patch sizes, confined to two dimensions, generate a series of patterns of interest to the field of nanoscience. Here we observe reverse melting, where for some densities the system melts under cooling. For a broad range of hydrophobic patch sizes (60^{∘}<θ_{0}<90^{∘}), a reentrant transition from solid to liquid and then to an ordered phase emerges as temperature (T) decreases due to the formation of rhombus chains at low T. This reentrant phase has pseudo long-range orientational order but short-range translational order, similar to a hexatic phase. Our work provides guidelines to study the melting and assembly of Janus particles in two dimensions, as well as mechanisms to generate phases with specific symmetry.