Dipolar Interactions Research Articles

Plasmon-enhanced chiral absorption through electric dipole–electric quadrupole interaction

Enantioselective interactions of chiral molecules include distinct absorptions to opposite-handed circularly polarized light, known as chiral absorption. Traditionally, chiral absorption has been primarily attributed to electric dipole (ED) and magnetic dipole (MD) interaction with molecular chirality. However, this approach falls short for large molecules that support high-order multipolar components, such as electric quadrupole (EQ) moment. Here, we introduce a theoretical model to study the chiral absorption of large molecules in the presence of plasmonic nanostructures. This model considers both ED–MD interaction and ED–EQ interaction enhanced by a resonant structure. We numerically study such interactions of the chiral molecular solution in the vicinity of an achiral plasmonic nano-resonator. Our results show the distinct spectral information of the chiral medium on- and off-resonance of the resonator.

Ordered States in Heisenberg Pyrochlore Antiferromagnets with Dipole–Dipole Interactions

Ordered States in Heisenberg Pyrochlore Antiferromagnets with Dipole–Dipole Interactions

Manipulation of Chiral Nonlinear Optical Effect by Light-Matter Strong Coupling.

Light-matter strong coupling (LMSC) is an intriguing state in which light and matter are hybridized inside a cavity. It is increasingly recognized as an excellent way to control material properties without any chemical modification. Here, we show that the LMSC is a powerful state for manipulating chiral nonlinear optical (NLO) effects through the investigation of second harmonic generation (SHG) circular dichroism. At the upper polariton band in LMSC, in addition to the enhancement of SHG by more than 1 order of magnitude, the responsivity to the handedness of circularly polarized light was largely modified, where sign inversion and increase of the dissymmetry factor were achieved. Quarter waveplate rotation analysis revealed that the LMSC clearly influenced the coefficients associated with chirality in the NLO process and also contributed to the enhancement of nonlinear magnetic dipole interactions. This study demonstrated that LMSC serves as a great platform for controlling chiral and magneto-optics.

A phenomenological model for chains and bands in dipolar suspensions

We introduce a phenomenological model for the dipolar interaction of polarizable particles under an external field, where the relative radial and rotational components of a particle pair interaction can be tuned. We show that the relative strengths of these two components govern the microstructure and dynamics of a suspension of such particles. Notably, dominant radial interactions give rise to the formation of zigzag band patterns, which were previously only thought to occur in systems where hydrodynamic interactions dominate. Through this phenomenological model, we show that dipolar interactions can be used to access an array of patterns in suspensions of polarizable particles, from chains to bands, which would dramatically affect suspension shear rheology, for instance.

Dynamics of Dipolar and Ionic Interactions in Self-Healable Poly(ionic liquid) Copolymers

Dynamics of Dipolar and Ionic Interactions in Self-Healable Poly(ionic liquid) Copolymers

Steady-state phases and interaction-induced depletion in a driven-dissipative chirally-coupled dissimilar atomic array

A nanophotonic waveguide coupled with an atomic array forms one of the strongly coupled quantum interfaces to showcase many fascinating collective features of quantum dynamics. In particular, for a dissimilar array of two different interparticle spacings with competing photon-mediated dipole-dipole interactions and directionality of couplings, we study the steady-state phases of atomic excitations under a weakly driven condition of laser field. We identify a partial set of steady-state phases of the driven system composed of combinations of steady-state solutions in a homogeneous array. We also reveal the intricate role of the atom at the interface of the dissimilar array in determining the steady-state phases and find an alteration in the dichotomy of the phases strongly associated with steady-state distributions with crystalline orders. We further investigate in detail the interaction-induced depletion in half of the dissimilar array, where the blockaded region results from two contrasting interparticle spacings near the reciprocal coupling regime. This can be further evidenced from the analytical solutions under the reciprocal coupling. Our results can provide insights in the driven-dissipative quantum phases of atomic excitations with nonreciprocal couplings and pave the avenues toward quantum simulations of exotic many-body states essential for quantum information applications. Published by the American Physical Society 2024

High-temperature Néel skyrmions in Fe3GaTe2 stabilized by Fe intercalation into the van der Waals gap

Two-dimensional (2D) van der Waals (vdW) magnets that exhibit ferromagnetism at ambient temperature show great promise for spintronic applications. However, until now, only a few pristine or doped 2D magnets have demonstrated the ability to host non-collinear spin textures, thereby limiting their potential applications. Here we directly observe Néel-type skyrmions in the metallic vdW magnetic compound Fe3GaTe2 (FGaT) up to temperatures well above room temperature (≈340 K) in the absence of any external magnetic field. We show that the presence of defects in the structure of FGaT make its structure acentric and therefore compatible with hosting skyrmions that would otherwise not be possible. Indeed, in this regard it is very similar to the closely related compound Fe3GeTe2 (FGT), whose structure with the same space group P3m1 is also realized by defects. Interestingly, however, FGaT accommodates a significantly higher concentration of Fe within the vdW gaps, likely accounting for its enhanced Curie temperature (TC). In addition to the Néel skyrmions observed in the temperature range of 250–340 K, we also detect type-I and -II Bloch-type skyrmionic bubbles in the temperature range of 100–200 K due to an enhanced magnitude of dipole-dipole interactions relative to the Dzyaloshinskii-Moriya exchange interaction. Self-intercalation is thus a highly interesting property of vdW magnets that considerably modifies their fundamental properties.

Temperature-dependent photoluminescence of novel Eu3+, Tb3+, and Dy3+ doped LaCa4O(BO3)3: Insights at low and room temperatures

This study explores the structural and optical qualities of LaCa4O(BO3)3 (LACOB) phosphors doped with Eu3+, Dy3+, and Tb3+ using a microwave-assisted sol-gel technique. It uncovers oxygen-related luminescence defects in LACOB, highlighting emission peaks at 489 and 585 nm for Dy3+, a distinct sharp peak at 611 nm for Eu3+ in the red spectrum, and a notable green emission for Tb3+ due to specific transitions. The photoluminescence (PL) analysis indicates that luminescence is optimized through precise doping, leveraging dipole interactions, and localized resonant energy transfer, which are influenced by dopant concentration and spatial configuration. Temperature studies show emission intensity variations, particularly noticeable below 100 K for Tb3+ doped samples, demonstrating the nuanced balance between thermal quenching and luminescence efficiency. This temperature dependency, alongside the identified optimal doping conditions, underscores the potential of these materials for advanced photonic applications, offering insights into their thermal behavior and emission mechanisms under different conditions.

An improved subtraction model applied in supercritical fluid chromatography to characterise polar stationary phases

Herein, an improved subtraction model was proposed to characterise the polar stationary phases in supercritical fluid chromatography (SFC). Fifteen stationary phases were selected, including two types of aromatic columns, Waters Torus and Viridis series columns, as well as silica and amino columns. Ethylbenzene and Torus 1-AA were defined as the reference solute and column, respectively. Identifying the interaction with the maximum contribution to retention in SFC separation and using it as the initial term is a key step in modelling. The dipole, or induced dipole interaction (θ′P), replaced the hydrophobic interaction (η′H) as the starting term. The improved model was expressed as logα=η′H+β′A+α′B+κ′C+θ′P+ε′E+σ′S, where the term ε′E indicated that anion exchange interaction was intentionally supplemented. A 7-step modelling process, including bidirectional fitting and residual analysis, was proposed. The obtained column parameters had reasonable physical significance, with the adjusted determination coefficient (R2adj) greater than 0.999 and the standard error (SE) less than 0.029. Methodological validation was further performed using the other four columns and 12 solutes that were not involved in the modelling. The result revealed good predictions of solutes’ retention, as demonstrated by R2adj from 0.9923 to 0.9979 and SE from 0.0636 to 0.1088. This study indicated the feasibility of using the improved subtraction model to characterise polar stationary phases in SFC, with the most crucial being the determination of an initial term, followed by the addition of a new descriptor and the selection of an appropriate reference column. The study expanded the application scope of the subtraction model in SFC, which will help gain an in-depth understanding of the SFC separation mechanism.

Novel Tb³⁺-Doped LaAl₂B₄O₁₀ phosphors: Structural analysis, luminescent properties, and energy transfer mechanism

This study explores the structural and luminescent properties of terbium (Tb³⁺)-doped lanthanum aluminium borate (LaAl₂B₄O₁₀, abbreviated as LAB) phosphors, a novel host lattice for Tb³⁺ doping. LAB:Tb³⁺ phosphors, with varying dopant concentrations, were synthesized using a microwave-assisted combustion synthesis approach and characterized using X-ray diffraction (XRD), Rietveld refinement, and photoluminescence spectroscopy at both room and low temperatures. The structural analysis confirmed the hexagonal crystal structure of LAB and revealed successful incorporation of Tb³⁺ ions without altering the fundamental lattice. Luminescence studies demonstrated that the LAB:Tb³⁺ phosphors show strong green emission primarily attributed to the 5D4→7F5 transition of Tb³⁺. The optimal doping concentration was determined to be 5 wt% Tb³⁺, which provided maximum luminescence efficiency. This concentration also allowed for a critical study of energy transfer mechanisms within the phosphor, revealing dipole-dipole interactions with a critical distance of 9.80 Å between Tb³⁺ ions. Additionally, the CIE chromaticity coordinates of LAB:0.05 Tb³⁺ were precisely determined to be (0.289, 0.4460), indicating the potential for high-quality green emission suitable for solid-state lighting and display technologies. This work not only demonstrates the potential of LAB:Tb3+ as a highly efficient green luminescent material, but also sheds light on the mechanisms responsible for energy transfer and concentration quenching.

Scalable Analysis of Dipole Moment Fluctuations for Characterizing Intermolecular Interactions and Structural Stability.

Accurately predicting protein-ligand interactions is essential in computational molecular biochemistry and in silico drug development. Monitoring changes in molecular dipole moments through molecular dynamics simulations provides valuable insights into dipole-dipole interactions, which are critical for understanding protein structure stability and predicting protein-ligand binding affinity. In this study, we propose a novel method to monitor changes in the interangle between dipole vectors of residue molecules within proteins and ligand molecules, aiming to evaluate the strength and consistency of interactions within the complex. Additionally, we extend the concept of positional root-mean-square fluctuation (RMSF), commonly used for protein structure stability analysis, to dipole moments, thus defining dipole moment RMSF. This enables us to analyze the stability of dipole moments for each residue within the protein and compare them across residues and between binding and non-binding complexes. Using the CRBP1-retinoic acid complex as our model system, we observed a significant difference in the interangle change of dipole moments for the key residue at the residue-level between the non-binding and binding complexes. Furthermore, we found that the dipole moment RMSF value of the non-binding complex was substantially larger than that of the binding complex, indicating greater dipole moment instability in the non-binding complex. Leveraging the concept of scalability inherent in the calculation of dipole moment vectors, we systematically expanded the residues within the protein's primary secondary structure. Our dipole moment analysis approach can provide valuable predictive insights into complex candidates, especially in situations where experimental comparisons are challenging.

Dispersion-driven cooperativity in alkyl perylenediimide oligomers: insights from densityfunctional theory.

The cooperative mechanism is of paramount importance in the synthesis of supramolecular polymers with desired characteristics, including molecular mass, polydispersity, and morphology. It is primarily driven by the presence of intermolecular interactions, which encompass strong hydrogen bonding, metal-ligand interactions, and dipole-dipole interactions. In this study, we utilize density functional theory and energy decomposition analysis to investigate the cooperative behavior of perylene diimide (PDI) oligomers with alkyl chains at their imide positions, which lack the previously mentioned interactions. Our systematic examination reveals that dispersion interactions originating from the alkyl side-chain substituents play an important role in promoting cooperativity within these PDIs. This influence becomes even more pronounced for alkyl chain lengths beyond hexyl groups. The energy decomposition analysis reveals that the delicate balance between dispersion energy and Pauli repulsion energy is the key driver of cooperative behavior in PDIs. Additionally, we have developed a mathematical model capable of predicting the saturated binding energies for PDI oligomers of varying sizes and alkyl chain lengths. Overall, our findings emphasize the previously undervalued significance of dispersion forces in cooperative supramolecular polymerization, enhancing our overall understanding of the cooperative mechanism.

Adhesive Zwitterionic Poly(ionic liquid) with Unprecedented Organic Solvent Resistance.

The resistance of adhesives to organic solvents is of paramount importance in diverse industries. Unfortunately, many currently available adhesives exhibit either weak intermolecular chain interactions, resulting in insufficient resistance to organic solvents, or possess a permanent covalent crosslinked network, impeding recyclability. This study introduces an innovative approach to address this challenge by formulating zwitterionic poly(ionic liquid) (ZPIL) derivatives with robust dipole-dipole interactions, incorporating sulfonic anions and imidazolium cations. Due to its unique dynamic and electrostatic self-crosslinking structure, the ZPIL exhibits significant adhesion to various substrates and demonstrates excellent recyclability even after multiple adhesion tests. Significantly, ZPIL exhibits exceptional adhesion stability across diverse nonpolar and polar organic solvents, including ionic liquids, distinguishing itself from nonionic polymers and conventional poly(ionic liquid)s. Its adhesive performance remains minimally affected even after prolonged exposure to soaking conditions. The study presents a promising solution for the design of highly organic solvent-resistant materials for plastics, coatings, and adhesives.

Tuning and high temperature fluorescence properties of LaPO4:Sm3+ nanophosphors

A series of LaPO4:x%Sm3+ nanophosphors were successfully synthesized through a one-step hydrothermal method, where the acidity of the reaction system was meticulously modulated without the addition of any organic compounds. The influence of pH values and Sm3+ doping concentration on the structure, morphology, and luminescent properties of LaPO4:x%Sm3+ was systematically investigated. The composition, structure, morphology, and luminescent properties of the products were characterized and analyzed using advanced techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM, EDS), transmission electron microscopy (TEM), and fluorescence spectrophotometry (FL). The results indicate that the acidity of the reaction system effectively influences the morphology and size of the nanophosphors, facilitating the controlled synthesis of nanorod-shaped, nano-spherical, and ellipsoidal phosphors. When the Sm3+ doping concentration is 2 %, the phosphors exhibit maximum luminescent intensity and fluorescence lifetime. The energy transfer between Sm3+ ions in LaPO4:x%Sm3+ is identified as electric dipole-electric dipole interaction, with a critical distance for energy transfer established at 1.593 nm. LaPO4:2%Sm3+ exhibits good thermal stability, characterized by a thermal quenching activation energy of 0.1660 eV. The main outcome of this research, LaPO4:2%Sm3+ phosphor, exhibits significant potential for use in optical sensors, as well as promising applications in solar cells and biological fields.

Spin angular momentum-encoded single-photon emitters in a chiral nanoparticle-coupled WSe2 monolayer.

Spin angular momentum (SAM)-encoded single-photon emitters, also known as circularly polarized single photons, are basic building blocks for the advancement of chiral quantum optics and cryptography. Despite substantial efforts such as coupling quantum emitters to grating-like optical metasurfaces and applying intense magnetic fields, it remains challenging to generate circularly polarized single photons from a subwavelength-scale nanostructure in the absence of a magnetic field. Here, we demonstrate single-photon emitters encoded with SAM in a strained WSe2 monolayer coupled with chiral plasmonic gold nanoparticles. Single-photon emissions were observed at the nanoparticle position, exhibiting photon antibunching behavior with a g(2)(0) value of ~0.3 and circular polarization properties with a slight preference for left-circular polarization. Specifically, the measured Stokes parameters confirmed strong circular polarization characteristics, in contrast to emitters coupled with achiral gold nanocubes. Therefore, this work provides potential insights to make SAM-encoded single-photon emitters and understand the interaction of plasmonic dipoles and single photons, facilitating the development of chiral quantum optics.

Investigations of structural, photoluminescence, colorimetric, lifetime, and luminous efficiency of Tb3+ and Sm3+ co-doped calcium tungstate for WLEDs

Structure, photoluminescence, colorimetric, and thermoluminescence analysis of Ca1-x-yTb2x/3Sm2y/3WO4; x = 0.01; y = 0.01–0.05 ceramics are reported in this manuscript. The materials are made by the use of the solid-state method. Reitveld refinements of the obtained X-ray diffraction patterns are done by using the Fullprof Suite software. The obtained results denoted that the synthesized materials have a tetragonal structure and I41/a space group. Energy bandgaps are found in the UV–visible absorbance spectra. Photoluminescence investigations of the phosphors are done. The critical quenching concentrations of the phosphor are found to be x = 0.01; and y = 0.04. Moreover, the critical distance of energy shift with the adjacently presented ions is computed. Dexter’s theory is employed to elucidate that the dipole-dipole electronic interactions are the imperative reasons for the transfer of energy in the phosphor. The white color of emission is achieved for x = 0.01, y = 0.04 Tb, and Sm doped CaWO4 material. Moreover, great values in color purity, correlated color temperature, color rendering index as well as luminous efficiency of radiation are obtained from the CIE Chromaticity coordinates. Quantum yield efficiency of x = 0.01, y = 0.04 Tb & Sm codoped CaWO4 is measured. Photoluminescence decay analysis of all the samples is done to study the long-after glow properties and also the average lifetime values are evaluated. This is an indication of the suitable usage of the prepared materials in the white light-emitting diodes. Concentration as well as dose-dependent Thermoluminescence spectroscopy is investigated thoroughly. Kinetic parameters are calculated by deconvoluting the spectra of x = 0.01; y = 0.01 Tb & Sm codoped CaWO4 irradiated with 15 min of UV excitation dose. These results are denoted by high trap depth, second-order kinetics, and low UV dosimetry of the phosphor.

Anapole source based on electric dipole interactions over a low-index dielectric

Anapole source based on electric dipole interactions over a low-index dielectric

Synthesis and high-frequency magnetoelectric characterization of the 0–3 particulate lead-free multiferroic composite KNN/CFO

The research for lead-free magnetoelectric (ME) multiferroic composite materials has increased considerably because they are environmentally friendly. For composites with 0–3 connectivity, synthesis with lead-free phase has proven challenging to obtain high values of ME coupling. This work reports the successful synthesis of the KNN/CFO composite (K0.5N0.5NbO3/CoFe2O4) by conventional synthesis process. XRD and SEI showed two well-defined, also presenting good electric polarization values. The ME coefficient was very high, reaching values close to 2850 mV cm−1·Oe at the electromechanical resonance frequency. The dipolar interaction between the electric charges and magnetic moments of the KNN and CFO phases was responsible for the high value and the behavior of dependence on the applied magnetic field.

Breakdown of steady-state superradiance in extended driven atomic arrays

Recent advances in generating well controlled dense arrangements of individual atoms in free space have generated interest in understanding how the extended nature of these systems influences superradiance phenomena. Here, we provide an in-depth analysis on how space-dependent light shifts and decay rates induced by dipole-dipole interactions modify the steady-state properties of coherently driven arrays of quantum emitters. We characterize the steady-state phase diagram, with particular focus on the radiative properties in the steady state. Interestingly, we find that diverging from the well-established Dicke paradigm of equal all-to-all interactions significantly modifies the emission properties. In particular, the prominent quadratic scaling of the radiated light intensity with particle number in the steady state—a hallmark of steady-state Dicke superradiance—is entirely suppressed, resulting in only linear scaling with particle number. We show that this breakdown of steady-state superradiance occurs due to the emergence of additional dissipation channels that populate not only superradiant states but also subradiant ones. The additional contribution of subradiant dark states in the dynamics leads to a divergence in the time scales needed to achieve steady states. Building on this, we further show that measurements taken at finite times for extended atom ensembles reveal properties closely mirroring the idealized Dicke scenario. Published by the American Physical Society 2024

Functionally Modified Polymer Electrolyte Based on Noncovalent Interaction for Stable Lithium Metal Batteries.

The charge transfer efficiency of the solid electrolyte depends on the number of lithium ions that can be effectively transported and participate in the electrode reaction. However, limited by the strong coupling relationship between Li+ and Lewis basic sites on the polymer chain, the Li+ transference number (tLi+) of the solid polymer electrolyte (SPE) based dual-ion conductor is typically low, resulting in excessive anion aggregation at the electrode side and inducing concentration polarization. In this study, we present a functionalized modified polymer electrolyte (FMPE) with selective cation transport, which was synthesized by embedding 4-(trifluoromethyl)styrene (TFS) functionalized groups onto the poly(diethylene glycol diacrylate) polymer chain. The TFS group formed noncovalent couplings with TFSI- anions through hydrogen bondings and dipole-dipole interactions, which effectively limited the migration of the anions and contributed to the elevated tLi+ of the FMPEs to 0.595 and 0.699 at 25 and 60 °C, respectively. Density functional theory (DFT) calculations were performed to verify the increased anion migration barriers for different noncovalent interactions and revealed that the conjugated system formed by the delocalized π electrons of the benzene ring and the C═O groups helped to disperse the electron distribution of the polymer chains. Consequently, the decrease in the degree of Li+ immobilization promotes the decoupling and migration of Li+ between the polymer chains. Benefiting from optimized Li+ transport behavior, the lithium metal batteries (LMBs) assembled by FMPEs and LiFePO4 exhibit excellent rate performance (discharge specific capacity of 88.8 mAh g-1 at 5 C) and stable long-term cycle performance (capacity decay rate of only 0.064% per cycle for 500 cycles at 25 °C and 0.5 C).