Dipolar Chains Research Articles

Electrical Quantum Coupling of Subsurface-Nanolayer Quasipolarons.

We perform dielectric and impedance spectrums on the compressively-strained ceramics of multiferroic bismuth ferrite. The subsurface-nanolayer quasipolarons manifest the step-like characteristic of pressure-dependent transient frequency and, furthermore, pressure-dependency fails in the transformation between complex permittivity and electrical impedance, which is well-known in classic dielectric physics, as well as the bulk dipole chain at the end of the dissipation peak.

In Ukrainian

Brownian motors belong to the class of nanoscale devices that use the thermal noise of the environment as one of the necessary components in the mechanism of their operation. Today, there are a lot of practical implementations of such nanomachines, both inorganic, fairly simple mechanisms produced artificially, and more complex ones created from separate biological components available at the cellular level. One of the options for implementing the mechanism of straightening the chaotic thermal noise of the environment into unidirectional motion is the presence of a motor particle in the field of action of an asymmetric periodic stationary potential, which undergoes certain small disturbances (fluctuations) periodically over time. To describe such asymmetric one-dimensional structures (for example, dipole chains or fibers of the cytoskeleton) in the theory of Brownian motors, two model potentials are most often used: piecewise linear sawtooth and double sinusoidal. In this work, within the framework of the approximation of small fluctuations, a model of a pulsating Brownian motor with a stationary double sinusoidal potential and a disturbing small harmonic signal is considered. A new method of parametrization of such a problem is proposed, which allows to separate the contributions from various factors affecting the operation of the ratchet, and the numerical procedure for calculating the average speed of the directional movement of nanoparticles for the selected type of model potentials is specified. A number of numerical dependences of the average speed on the main parameters of the system were obtained. Peculiarities of the behavior of the motor as dependent on the parameter responsible for asymmetry and the number of potential wells on the spatial period of the stationary potential have been investigated. It is shown that the direction of the generated flux of nanoparticles depends not only on the phase shift between the stationary and fluctuating components of the potential, but also on the temperature of the system and the frequency of fluctuations, i.e., a possibility of temperature-frequency control of the direction of movement in the considered model has been found. Diagrams have been constructed that allow you to choose the ratio between the parameters of the nanomotor to create a flux of particles in the desired direction.

Ground states of planar dipolar rotor chains with recurrent neural networks

In this contribution, we employ a recurrent neural network (RNN) architecture in a variational optimization to obtain the ground state of linear chains of planar, dipolar rotors. We test different local basis sets and discuss their impact on the sign structure of the many-body ground state wavefunction. It is demonstrated that the RNN ansatz we employ is able to treat systems with and without a sign problem in the ground state. For larger chains with up to 50 rotors, accurate properties, such as correlation functions and Binder parameters, are calculated. By employing quantum annealing, we show that precise entanglement properties can be obtained. All these properties allow one to identify a quantum phase transition between a paraelectric and a ferroelectric quantum phase.

The dipolar Schramm-Loewner equation for finitely many slits

Let Σ be any disjoint union of finitely many simple curves in the strip region. Based on the continuous dependence of dipolar Loewner chains and the pre-compactness of driving functions associated with subhulls of Σ, it is derived that Σ can be generated from a dipolar Schramm-Loewner equation with constant weights. Moreover, using the estimates of derivatives of strip-capacity it is showed that the corresponding weights and driving functions are uniquely determined by Σ. This generalizes dipolar Schramm-Loewner equation for 1-slit to the case of one for multiple slits.

The relevance of curvature-induced quadrupolar interactions in dipolar chain aggregation.

The aggregation of dipolar chains driven by thermal fluctuations in an external strong (electric or magnetic) field is investigated theoretically. We discover a new simple electrostatic mechanism that rationalizes the counter-intuitive lateral coalescence of dipolar chains. There, we first demonstrate that two bent dipolar chains can either attract or repel each other depending if they possess similar or opposite curvatures, respectively. Upon bending, dipolar chains become the siege of polarization-induced local charges that in turn lead to quadrupolar couplings. This striking feature is then exploited to understand our conducted Monte Carlo simulations at finite temperature where thermal fluctuations cause local curvatures in the formed dipolar chains. The related quadrupolar attractive mode with correlated chain-curvatures is clearly identified in the simulation snapshots. Our findings shed new light on a longstanding problem in soft matter and related areas.

Conformational Behavior of a Single Dipolar Chain under Stretching Force

Conformational Behavior of a Single Dipolar Chain under Stretching Force

Synthesis and mesomorphic properties of bent liquid crystals containing triazole mesogenic unit with terminal flexible alkyl chain and laterally ethoxy substituted Schiff base

ABSTRACT A new series of bent-shaped liquid crystals containing a triazole ring were synthesised and characterised at ambient and elevated temperatures. The triazole-cored and bent liquid crystals possess a flexible alkyl chain at one terminal, while the other side of the core is connected by a laterally ethoxy Schiff base consisting of a CN-biphenyl moiety. The evaluation on optical and thermal properties was carried out by polarising optical microscope and differential scanning microscope which revealed the length of the alkyl chain, –CnH2n + 1, that influenced the mesophase and the related clearing temperatures (Tc). Whilst the compounds with higher number of n possess lower Tc points, the presence of SmA phase seemed to be more favourable for the compounds in which the alkyl chain length was n ≥ 12. This observation can be associated with its bending angle and charge distributions along the two arms of which the interaction between the opposite counterparts of both arms in these bent-liquid crystals would promote the formation of SmA phase. The computational calculations based on density functional theory were performed to further support the transition from non-mesomorphic to SmA phases upon the increase in alkyl chain length (n), dipole moment and polarity which contribute to its stability.

Local analysis of crystalline phases and properties of poly(vinylidene fluoride) electrospun composites with BaTiO3 nanorods

AbstractThis study investigated the influence of barium titanate nanorods (BT rods) on the properties and phase formation of poly(vinylidene fluoride) (PVDF) nanofibers of composite membranes created using the electrospinning technique. The primary objective was to assess the effect of varying BT nanorod concentrations on the membrane properties. The result shows that inserting BT rods into PVDF increases β‐phase content, which, with an optimal concentration of BT rods, affects the activation energy of thermal degradation resulting in the highest β‐phase content and the lowest activation energy at 3% BT content. Moreover, the electrical output of the samples was measured. Using a ball‐drop test, the sample containing 3 wt% BT rods exhibited the highest output voltage, reaching 1.64 V. The BT rods play a significant role in promoting the β‐phase PVDF molecular chain formation, acting as the polar phase in PVDF and aligning with the polarization direction of the BT rods. According to high‐resolution transmission electron microscopy investigations, crystalline phases of PVDF are strongly correlated with the surface charges of perovskite BT rods. The occurrence of charge on the BT rods significantly contributes to fostering the development of the β‐phase PVDF molecular chain. It essentially performs the function of the polar phase within the PVDF, aligning itself in accordance with the polarization direction inherent to the BT rods. In conclusion, this study demonstrates the potential of incorporating BT rod polar surfaces to interact with PVDF chain dipole moments, promoting β‐phase formation. © 2023 Society of Industrial Chemistry.

A gradient micromechanical model to explore flexoelectric copolymers via stochastic chain growth

Flexoelectric sensors respond with an electric polarization when they are subjected to inhomogeneous deformation. When these are based on polymeric materials, the electro-mechanical coupling relates to the loss of microstructural symmetries of the polar polymer chains. The object of this work is to explore the mechanisms that induce flexoelectricity in soft (co)polymers via a micromechanical model that explicitly considers the spatial composition distribution of polymer chains. To this end, we analyze the deformation of the Arruda–Boyce 8-chain cell under inhomogeneous deformation and its influence on the overall polarization resulting from the polar monomers. Cells with random-walk chains and tailored degree of entanglement feed Monte Carlo simulations to inform an effective chain dipole that drives the flexoelectric polarization. Homogeneous stretch/compression of the cell accompanying bending deformation reinforce the flexoelectric response. In addition, we focus on stochastic chain-growth processes and the insertion of different types of polar monomers within a same chain. Here, we introduce a model where reactivity ratios of real copolymerization reactions control the resulting flexoelectric coupling. Since the framework allows to relate the effective flexoelectric polarization to any structural isomer distribution, it is especially convenient to model copolymers. Overall, the model is proposed as a versatile framework to explore the intricacies of flexoelectric (co)polymers and to foster the design of flexoelectric devices from real manufacturing parameters.

Fate of Magnetic Nanoparticles during Stimulated Healing of Thermoplastic Elastomers.

We have investigated the heating mechanism in industrially relevant, multi-block copolymers filled with Fe nanoparticles and subjected to an oscillatory magnetic field that enables polymer healing in a contactless manner. While this procedure aims to extend the lifetime of a wide range of thermoplastic polymers, repeated or prolonged stimulus healing is likely to modify their structure, mechanics, and ability to heat, which must therefore be characterized in depth. In particular, our work sheds light on the physical origin of the secondary heating mechanism detected in soft systems subjected to magnetic hyperthermia and triggered by copolymer chain dissociation. In spite of earlier observations, the origin of this additional heating remained unclear. By using both static and dynamic X-ray scattering methods (small-angle X-ray scattering and X-ray photon correlation spectroscopy, respectively), we demonstrate that beyond magnetic hysteresis losses, the enormous drop of viscosity at the polymer melting temperature enables motion of nanoparticles that generates additional heat through friction. Additionally, we show that applying induction heating for a few minutes is found to magnetize the nanoparticles, which causes them to align in dipolar chains and leads to nonmonotonic translational dynamics. By extrapolating these observations to rotational dynamics and the corresponding amount of heat generated through friction, we not only clarify the origin of the secondary heating mechanism but also rationalize the presence of a possible temperature maximum observed during induction heating.

Correction to “Side Chain Dipole Orientation and Its Effect on Microphase Separation: Experiment and Simulation via Structural Isomer Variation”

Correction to “Side Chain Dipole Orientation and Its Effect on Microphase Separation: Experiment and Simulation via Structural Isomer Variation”

Side Chain Dipole Orientation and Its Effect on Microphase Separation: Experiment and Simulation via Structural Isomer Variation

We use experiments and molecular dynamics simulations in an investigation of structural isomer–property relationships in block copolymers (BCPs) that allow us to isolate the effects of dipole orientation on microphase separation and χ. We combine anionic polymerization of a single parent BCP with post-polymerization thiol-epoxy “click” chemistry with a series of structural isomers of fluorinated thiophenols to synthesize structural isomeric BCPs (SI-BCPs). The resulting SI-BCPs possess identical molecular weight and dispersity, such that only the isomerism can affect microphase separation. Domain periodicity of the SI-BCPs is measured with small angle X-ray scattering, from which χ is estimated. The value of χ for each SI-BCP shows a significant dependence on the position of fluorine atoms on the phenyl ring of the thiophenol. Simulation results show a strong correlation between the dipole moment orientation of the appended thiol and χ, which is also observed in simulations of a BCP of the structural isomers poly(2-vinylpyridine) and poly(4-vinylpyridine). This work illustrates a little-known facet of the structure–property relationship of BCP materials and provides another tool for the molecular engineering of BCPs.

Biodegradable MOFilters for Effective Air Filtration and Sterilization by Coupling MOF Functionalization and Mechanical Polarization of Fibrous Poly(lactic acid).

High-performance air filtration materials are important for addressing the airborne pollutants. Herein, we propose an unprecedented access to biodegradable poly(lactic acid) (PLA)-based MOFilters with excellent filtering performance and antibacterial activity. The fabrication involved a stepwise in situ growth of zeolitic imidazolate framework-8 (ZIF-8) crystals at the surface of microfibrous PLA membranes, followed by mechanical polarization under high pressure and low temperature (5 MPa, 40 °C) to trigger the ordered alignment of dipoles in PLA chains and ZIF-8. The unique structural features allowed these PLA-based MOFilters to achieve an exceptional combination of excellent tensile properties, high dielectric constant (up to 2.4 F/m), and enhanced surface potential as high as 4 kV. Arising from the remarkable surface activity and electrostatic adsorption effect, a significant increase (from over 12% to nearly 20%) in PM0.3 filtration efficiency was observed for the PLA-based MOFilters compared to that of pure PLA counterparts, with weak relation to the airflow velocities (10-85 L/min). Moreover, the air resistance was controlled at a considerably low level for all the MOFilters, that is, below 183 Pa even at 85 L/min. It is worth noting that distinct antibacterial properties were achieved for the MOFilters, as illustrated by the inhibitive rates of 87 and 100% against Escherichia coli and Staphylococcus aureus, respectively. The proposed concept of PLA-based MOFilters offers unprecedented multifunction integration, which may fuel the development of biodegradable versatile filters with high capturing and antibacterial performances yet desirable manufacturing feasibility.

An economical smoke chamber and light-sheet microscope system for experiments in fluid dynamics and electrostatics

A smoke chamber and light-sheet video microscope setup is relatively easy to construct and provides opportunities for undergraduates to participate in a variety of advanced experiments, including the demonstration of Brownian motion and the interaction of induced electrostatic dipoles in aerosol particle agglomeration. We present results of these experiments along with information to allow replication of the setup in undergraduate physics laboratories. A theoretical model of the rate of aerosol agglomeration of long dipole chains as a function of electric field agrees with experiments at field strengths up to 200 kV m−1.

Nanoencapsulation-Induced Second Harmonic Generation in Pillararene-Based Host-Guest Complex Cocrystals.

The features of molecularly preferable centrosymmetric arrangements exclude organic nonlinear optical (NLO) materials for second harmonic generation (SHG) when used in the solid and crystalline states, which greatly limits their applications in optoelectronic devices. Herein, a pillar[5]arene (BrP5) is used as the macrocyclic host to encapsulate NLO molecules, 4-[4'-methoxystyryl]-1-methylpyridinium iodide (OM), 4-[2'-(5'-(dimethylamino)thiophen-2'-yl)vinyl]-1-methylpyridinium iodide (DAST), and 4-methoxy-β-nitrostyrene (MNS), to alter the solid-state packing of these NLO molecules and manipulate their centrosymmetric arrangements. BrP5 forms 2:1 host-guest complexes with OM and DAST, while it forms a 1:1 host-guest complex with MNS. Experimental results show that the pillar[5]arene and each of these three NLO guests form a nanocapsule architecture along with an overall centrosymmetric crystal structure. However, the random orientation of OM and DAST molecules inside the 2:1 host-guest complex nanocapsules breaks the local centrosymmetric arrangement of the NLO molecules, resulting in strong SHG. On the contrary, for BrP5⊃MNS, the MNS molecules inside the pillar[5]arene cavities are unable to break the centrosymmetry. They have only one determined orientation in the one-dimensional (1D) channels of BrP5, while other MNS molecules in adjacent channels have the opposite direction. The centrosymmetry of the dipolar chains is strictly maintained with the cancellation of nonlinear polarization, resulting in the quenching of SHG. Furthermore, an ultrasound-induced host-guest crystallization method is developed for the fast preparation of these host-guest composite materials with NLO activity. This work opens a new way to construct solid-state organic NLO materials, which have potential in high-power lasers, optical switches, and imaging applications.

Thermally and Magnetically Programmable Hydrogel Microactuators.

The rapid development in micro-machinery enabled the investigation of smart materials that can embody fast response, programmable actuation, and flexibility to perform mechanical work. Soft magnetic actuators represent an interesting platform toward combining those properties. This study focuses on the synthesis of micro-actuators that respond to thermal and magnetic stimuli using micro-molding with a soft template as a fabrication technique. These microsystems consist of a hydrogel matrix loaded with anisotropic magnetic nanospindles. When a homogeneous magnetic field is applied, the nanospindles initially dispersed in monomer solution, align and assemble into dipolar chains. The ensuing UV-polymerization creates a network and conveniently arrests these nanostructures. Consequently, the magnetic dipole moment is coplanar with the microgel. Varying the shape, volume, and composition of the micro-actuators during synthesis provides a temperature-dependent control over the magnetic response and the polarizability. Beyond isotropic swelling, shaping the hydrogel as long thin ribbons with a passive layer on one side allows for differential swelling leading to bending and twisting deformations, for example, 2D- or 3D-spiral. These deformations involve a reversible amplification of the magnetic response and orientation of the hydrogels under magnetic field. Temperature control herewith determines the conformation and simultaneously the magnetic response of themicro-actuators.

Disorder-enhanced transport in a chain of lossy dipoles strongly coupled to cavity photons

We study the interplay between disorder and light-matter coupling by considering a disordered one-dimensional chain of lossy dipoles coupled to a multimode optical cavity, through a microscopically derived Hamiltonian. Such a system, hosting polaritonic excitations, may be realized experimentally in a wide range of platforms under strong light-matter coupling. By analyzing both the eigenspectrum and the driven-dissipative transport properties of our system, we find that in the strong-coupling regime, increasing disorder leads almost uncoupled dark states to acquire a photonic part, allowing them to inherit polaritonic long-range transport characteristics. Crucially, we show that this disorder-enhanced transport mechanism is increasingly noticeable when the considered dipoles are lossier.

Directed walk in probability space that locates mean field solutions to spin models.

Despite their formal simplicity, most lattice spin models cannot be easily solved, even under the simplifying assumptions of mean field theory. In this paper, we present a method for generating mean field solutions to classical continuous spins. We focus our attention on systems with nonlocal interactions and nonperiodic boundaries, which require careful handling with existing approaches, such as Monte Carlo sampling. Our approach utilizes functional optimization to derive a closed-form optimality condition and arrive at self-consistent mean field equations. We show that this approach significantly outperforms conventional Monte Carlo sampling in convergence speed and accuracy. To convey the general concept behind the approach, we first demonstrate its application to a simple system: a finite one-dimensional dipolar chain in an external electric field. We then describe how the approach naturally extends to more complicated spin systems and to continuum field theories. Furthermore, we numerically illustrate the efficacy of our approach by highlighting its utility on nonperiodic spin models of various dimensionality.

Energy scale of dielectric coupling in antiferromagnetic insulators

To probe the energy of dielectric coupling between the dipole chains and the quasipolarons based on extension of the polaron concept, dielectric and magnetic properties of antiferromagnetic insulators, namely Ca4-xCuxTi4O12 (x = 3, 2 and 1), are investigated at different temperatures. The energy is estimated larger than 56 meV of the dipole interaction energy, but smaller than 88 meV of the dipole-chain thermal activation energy which is for the Dissado-Hill type dielectric relaxation. In particular, the quasipolaron ingredient is at least 28 meV of the total superexchange interaction which bond one singe titanium ion of the dipole chain with four quasipolarons. Then, the energy of the coupling is in the range from 84 meV to 88 meV. The experimental observation, suggests the dielectric coupling may provide an approach to obtain large permittivity in strongly-correlating systems of antiferromagnetic insulators.

Formation and crossover of multiple helical dipole chains

We investigate the classical equilibrium properties and metamorphosis of the ground state of interacting dipoles with fixed locations on a helix. The dipoles are shown to align themselves along separate intertwined dipole chains forming single, double, and higher-order helical chains. The number of dipole chains, and their properties such as chirality and length scale on which the chains wind around each other, can be tuned by the geometrical parameters. We demonstrate that all possible configurations form a self-similar bifurcation diagram which can be linked to the Stern–Brocot tree and the underlying Farey sequence. We describe the mechanism responsible for this behavior and subsequently discuss corresponding implications and possible applications.