Dipole Moment Research Articles

Interlayer excitons diffusion and transport in van der Waals heterostructures

Abstract The assembly of monolayer transition metal dichalcogenides (TMDs) in Van der Waals heterostructures yields the formation of spatially separated interlayer excitons (IXs) with large binding energies, long lifetimes, permanent dipole moments and valley-contrasting physics, providing a compelling platform for investigating and engineering spatiotemporal IX propagation with highly tunable dynamics. Further twisting the stacked TMD monolayers can create long-term periodic moiré patterns with spatially modified band structures and varying moiré potentials, featuring tailored traps that can induce strong correlations with density-dependent phase transitions to modulate the exciton transport. The rich exciton landscapes in TMD heterostructures, combined with advancements in valleytronics and twistronics, hold great promise for exploring exciton-integrated circuits base on manipulation of exciton diffusion and transport. In this Review, we provide a comprehensive overview of recent progress in understanding IXs and moiré excitons, with a specific focus on emerging exciton diffusion and transport in TMD heterostructures. We put emphasis on spatial manipulation of exciton flux through various methods, encompassing exciton density, dielectric environment, electric field and structure engineering, for precise control. This ability to manipulate exciton diffusion opens up new possibilities for interconverting optical communication and signal processing, paving the way for exciting applications in high-performance optoelectronics, such as excitonic devices, valleytronic transistors and photodetectors. We finally conclude this Review by outlining perspectives and challenges in harnessing IX currents for next-generation optoelectronic applications.

QuSpin zero-field magnetometer characterization for the TUCAN experiment

Abstract The TUCAN neutron electric dipole moment experiment utilizes the QuSpin Zero-Field Magnetometer (QZFM) to accurately map residual fields within a large magnetically shielded room. Three potential flaws of the QZFM are characterized in preparation for mapping. The magnetometer’s intrinsic offset was measured to be within ± 3 nT and stable over a period of one year. The response was shown to be within 2 percent of linearity in the zero-field regime, up to 2 nT pp , and then follows a smooth dispersion curve. Crosstalk effects induced by multisensor operation were determined to have a small effect, and inconsequential with a separation above 6 cm. These results enable the QZFM for accurate measurement of DC fields, increase the operational range of QZFM by a factor of more than an order of magnitude, and allow for higher efficiency and flexibility by green-lighting simultaneous operation of multiple QZFMs.

Axion production via trapped misalignment from Peccei-Quinn symmetry breaking

The Peccei-Quinn (PQ) symmetry does not need to be exact, and even a tiny source of PQ breaking not aligned with the QCD anomaly might have significant phenomenological implications. In this study, we examine the effects of a general class of PQ-breaking operators on the axion cosmological production via misalignment, focussing on both temperature-dependent and independent PQ-breaking potentials. In particular, we show that a variant of the trapped misalignment mechanism can delay the onset of axion oscillation, leading to an axion dark matter window with ma ≫ 10−5 eV. This scenario is testable through various experimental approaches, including standard axion haloscopes and helioscopes, as well as searches for electric dipole moments and axion-mediated forces.

Solvatochromism, electric dipole moments, optical properties and electronic structure of biphenylcarbonitrile liquid crystals

The UV–Vis. absorbance and fluorescence spectra of 4HC (4′-heptyl-4-biphenyl carbonitrile) and 4OB (4′-Octyl-4-biphenylcarbonitrile) liquid crystals were measured in 23 solvents with different polarities. As dependent on changing of solvents, while the change in absorbance spectrum of liquid crystals have less, change in fluorescence spectrum have more. Molecular interactions were quantitavely investigated by using Linear solvation energy relationships. Optical forbidden energy gap has been determined with using Tauc plot. The refractive index has been calculated with semi-empirical methods. The relationships between refractive index and Eg has been commented in n-hexane, acetic acid, water and 1,4-dioxane. The electric dipole moment has been calculated by using the Bilot-Kawski, Lippert-Mataga, Bakshiev, Kawski-Chamma-Viallet and Reichardt methods. Solvatochromic shifts showed to having large dipole moments of 4OB and 4HC LCs. Their molecular orbital energies, electric dipole moments, MEP, SAS, and reactivity properties of 4HC and 4OB LCs has been found by quantum chemical calculations. It was observed that the dipole moment of 4HC was higher than 4OB.

Organic Chimeras based on Selenosugars, Steroids, and Fullerenes as Potential Inhibitors of the β-amyloid Peptide Aggregation.

The aggregation of β-amyloid peptide (Aβ) is associated with neurodegenerative diseases such as Alzheimer's disease (AD). Several therapies aimed at reducing the aggregation of this peptide have emerged as potential strategies for the treatment of AD. This paper describes the design and preparation of new hybrid molecules based on steroids, selenosugars, and [60]fullerene as potential inhibitors of Aβ oligomerization. These moieties were selected based on their antioxidant properties and possible areas of interaction with the Aβ. Cyclopropanations between C60 and malonates bearing different steroid and selenosugar moieties using the Bingel-Hirsch protocol have enabled the synthesis of functionalized molecular hybrids. The obtained derivatives were characterized by physical and spectroscopic techniques. Theoretical calculations for all the selenium compounds were performed using the density functional theory DFT/B3LYP-D3(BJ)/6-311G(2d,p) predicting the most stable conformations of the synthesized derivatives. Relevant geometrical parameters were investigated to relate the stereochemical behavior and the spectroscopic data obtained. The affinity of the compounds for Aβ-peptide was estimated by molecular docking simulation, which predicted an increase in affinity and interactions for Aβ for the hybrids containing the C60 core. In addition, parameters such as lipophilicity, polar surface area, and dipole moment were calculated to predict their potential interaction with membrane cells.

Spontaneous Magnetization Induced by Antiferromagnetic Toroidal Ordering.

The magnetic toroidal dipole moment, which is induced by a vortex-type spin texture, manifests itself in parity-breaking physical phenomena, such as a linear magnetoelectric effect and nonreciprocal transport. We elucidate that a staggered alignment of the magnetic toroidal dipole can give rise to spontaneous magnetization even under antiferromagnetic structures. We demonstrate the emergence of uniform magnetization by considering the collinear antiferromagnetic structure with the staggered magnetic toroidal dipole moment on a bilayer zigzag chain. Based on the model calculations, we show that the interplay between the collinear antiferromagnetic mean field and relativistic spin-orbit coupling plays an important role in inducing the magnetization.

Fluorescence by incoherently pumped polar quantum dot placed in a low-frequency monochromatic field

Abstract We studied spectral properties of high-frequency fluorescent radiation from a two-level quantum system with broken inversion spatial symmetry, which can be implemented as a model of a one-electron two-level asymmetric polar semiconductor quantum dot whose electric dipole moment operator has permanent unequal diagonal matrix elements. The case of the excitation of this system by incoherent pumping of some sort supplemented with an additional driving monochromatic field, which frequency is much lower than the optical transition frequency of the quantum dot, was considered. An analytical expression for the fluorescence spectrum as a function of the amplitude and frequency of the monochromatic driving field, as well as of the pumping intensity, was derived. We also discussed feasible practical applications of the effects under study in the field of quantum optics and optoelectronics for the generation of high-frequency radiation, possessing stationary equidistant spectrum, and for the control of the radiative properties of such nanodevices as spasers (dipole nanolasers).

Synthesis, Crystal Structure, Intermolecular Interactions, HOMO-LUMO, MEP, NLO Properties, and DFT/TD-DFT Investigation of (Z)-5-(4-Nitrobenzylidene)-3-N(3-Chlorophenyl)-2-Thioxothiazolidin-4-One

A novel heterocyclic compound named (Z)-5-(4-nitrobenzylidene)-3-N(3-chlorophenyl)-2-thioxothiazolidin-4-one (NCTh) was synthesized and analyzed using various techniques, including single crystal X-ray diffraction, FT-IR, UV-Vis, NMR spectroscopy, and mass spectral data methods. NCTh was observed to crystallize in the triclinic crystal system P-1 space group. To validate the experimental findings, density functional theory (DFT) calculations were performed using the B3LYP functional with the 6-311 G(d,p) basis set. The results indicated good agreement in geometrical parameters between the experimental and theoretical outcomes. The study also calculated HOMO-LUMO energies, molecular electrostatic potential (MEP), and global chemical reactivity descriptors to evaluate the compound’s reactivity. Additionally, the study conducted reduced density gradient and Hirshfeld surface analyses to reveal attractive, repulsive, and van der Waals strong and weak interactions. The calculation of thermodynamic parameters was also included. The study focused on investigating the nonlinear optical (NLO) properties of NCTh, which were characterized through key parameters such as the electric dipole moment (µ), polarizability (α), first-order hyperpolarizability (β), and second-order hyperpolarizability (γ). These properties provide insights into the material’s potential applications in optical and photonic technologies. Additionally, a molecular docking study was performed to further explore the structure-activity relationship, particularly in a biological context. The docking results revealed a strong ligand-protein interaction, with a binding energy of −10.3 kcal/mol, indicating significant affinity. Moreover, the inhibition constant (Ki) was calculated to be 0.0281 μM, suggesting a highly potent interaction, which could be relevant for drug design or biochemical applications.

Nonhalogenated Solvent-Processed Efficient Ternary All-Polymer Solar Cells Enabled by the Introduction of a Naphthyloxy Group into the Side Chain of Polymer Donors.

Conjugated polymer donors are crucial for enhancing the power conversion efficiencies (PCEs) in all-polymer solar cells (All-PSCs) in nonhalogenated solvents. In this work, three wide-band-gap polymer donors (Sil-D1, Ph-Sil-D1, and Nap-Sil-D1) based on dithienobenzothiadiazole (DTBT) and benzodithiophene (BDT) donor moieties optimized by side chain engineering were designed and synthesized. Alkyl (Sil-D1), phenyloxy (Ph-Sil-D1), and naphthyloxy (Nap-Sil-D1) alkyl siloxane side chain units were incorporated into these polymer donors, respectively. Notably, the Nap-Sil-D1 polymer donor had a greater conjugation length, π-electron delocalization, and improved dipole moment. The deepest highest occupied molecular orbital level of Nap-Sil-D1, with a high absorption coefficient, showed better aggregation properties. In addition, reduced bimolecular recombination and trap-state density generated a high charge transfer to cause a significant enhancement of open-circuit voltage, current density, and fill factor values of 0.94 V, 25.5 mA/cm2, and 70.4%, respectively, for the Nap-Sil-D1-blended All-PSC ternary device (PM6:Nap-Sil-D1:PY-IT), with the highest PCE of 16.8% in the o-xylene solvent, compared to other polymers (Sil-D1 and Ph-Sil-D1) with PCEs of 15.5 and 16.2%. As a result, this optimized device architecture was found to be the most promising as a nonhalogenated solvent processed in additive-free ternary All-PSCs with good stability.

A computational study and analysis of Variational Quantum Eigensolver over multiple parameters for molecules and ions

AbstractMaterial discovery is a phenomenon practiced since the evolution of the world. The discovery of materials has led to significant development in varied fields such as Science, Engineering and Technology. Computationally simulating molecules has been an area of interest in the industry as well as academia. However, simulating large molecules can be computationally expensive in terms of computing power and complexity. Quantum computing is a recent development that can improve the efficiency in predicting properties of atoms and molecules which will be useful for material design. The Variational Quantum Eigensolver (VQE) is one such quantum algorithm used to calculate the ground state energy of molecules or ions. In this study, we have done a comparative analysis of the parameters that constitute the VQE algorithm. This includes components such as basis, qubit mapping, ansatz, and optimizers used. We have also developed a database consisting of 79 single atoms and their variations of oxidation states and 33 molecules with the data of their Hamiltonian and ground state energy and dipole moment.

Polar-Layer-Driven Reconstruction of a Noncentrosymmetric Vandate Mid-Infrared Nonlinear-Optical Crystal.

Noncentrosymmetry (NCS) is essential for a second-harmonic nonlinear-optical (NLO) crystal; however, the tailored synthesis of NCS materials has historically posed significant challenges because the adjacent dipole moments of constituted NLO-active units in the structure tend to align in opposite directions, resulting in the NLO effect being canceled as in a centrosymmetric (CS) crystal. In this work, we propose a polar-layer-driven strategy, wherein a polarization-layered framework is constructed to constrain the dipole moment to align in the same direction, thereby facilitating the formation of the NCS structure. Taking the layered structure CS K2ZnV2O7 as a prototype compound, a novel vandate K4ZnV5O15Br (KZVB) was rationally synthesized via a multiple sites-oriented cosubstition method. KZVB containing two types of NLO-active units of V5+ d0 and Zn2+ d10 cations can be utilized as a mid-infrared NLO crystal with a remarkable NLO response comparable to that of nonoxide AgGaS2. This work not only broadens the effective strategy for designing novel NCS compounds but also provides a progressive development of NLO materials.

Copper Atom Pairs Stabilize *OCCO Dipole Toward Highly Selective CO2 Electroreduction to C2H4

AbstractDeeply electrolytic reduction of carbon dioxide (CO2) to high‐value ethylene (C2H4) is very attractive. However, the sluggish kinetics of C−C coupling seriously results in the low selectivity of CO2 electroreduction to C2H4. Herein, we report a copper‐based polyhedron (Cu2) that features uniformly distributed and atomically precise bi‐Cu units, which can stabilize *OCCO dipole to facilitate the C−C coupling for high selective C2H4 production. The C2H4 faradaic efficiency (FE) reaches 51 % with a current density of 469.4 mA cm−2, much superior to the Cu single site catalyst (Cu SAC) (~0 %). Moreover, the Cu2 catalyst has a higher turnover frequency (TOF, ~520 h−1) compared to Cu nanoparticles (~9.42 h−1) and Cu SAC (~0.87 h−1). In situ characterizations and theoretical calculations revealed that the unique Cu2 structural configuration could optimize the dipole moments and stabilize the *OCCO adsorbate to promote the generation of C2H4.

Theoretical investigation on the surrounding effects of second-order nonlinear properties for (N^C^N)Pt(II)Cl complexes

Pt(II) complexes are widely used as nonlinear optical (NLO) materials. The geometric and electronic structures, second-order NLO property and UV–Vis absorption spectra of (N^C^N)Pt(II)Cl complexes (1–4) N^C^N binding by central benzene and two lateral N-heterocycles) are evaluated by density functional theory (DFT) and time-dependent DFT calculations. The detailed environmental effect of total first hyperpolarizability (βtot) in the solution and crystal phases is simulated by polarized continuum model (PCM) and quantum mechanics/molecular mechanics (QM/MM) method, respectively. The results highlight that the complex 3 exhibits largest βtot value in the gas, solution and crystal phases which can be attributed to the higher electron π-delocalization of ligands. Further, an evident red shift towards longer wavelength is observed for the complex 3. The origin of larger βtot value can be reasonably interpreted by the two-level model. In addition, the surrounding exerts an important influence on modulating second-order NLO properties. The solvent effect results in the larger βtot value than that of gas phase. The intermolecular interaction plays an important role in crystal phase. The formation of dimer can reduce the βtot value in comparison with the βtot value of the monomer in the crystal phase, because the centrosymmetric configuration of dimer implies a decrease of dipole moment (μ) in contrast to the large μ value of monomer. It is expected that this work will provide some guidance for designing Pt(II) NLO materials.

Determination of the Dipole Moment Variation Upon Excitation in the Chromophore of Green Fluorescent Protein From Molecular Dynamic Trajectories with QM/MM Potentials Using Machine Learning Methods

Quantum and molecular mechanics (QM/MM) potentials are used to calculate molecular dynamics trajectories for the EYFP protein of the green fluorescent protein family. Machine learning models are constructed to establish the relationship between the geometric parameters of the chromophore in the frame of its trajectory and the properties of its electronic excitation. It is shown that it is not enough to use only bridging bonds between the phenyl and imidazolidone fragments of the chromophore as a geometric parameter, and at least two more neighboring bonds must be added to the model. The proposed models allow determination of the dipole moment variation upon excitation with an average error of 0.11 a.u.

Ultrahigh Energy Storage of Twisted Structures in Supramolecular Polymers.

Polymer dielectrics possess outstanding advantages for high-power energy storage applications such as high breakdown strength (Eb) and efficiency (η), while both of them decrease rapidly at elevated temperatures. Although several strategies have been evaluated to enhance Eb and heat resistance, the discharged energy density (Ud) is still limited by the planar conjugated structure. In this study, a novel approach to manipulate polymer morphology is introduced, thereby influencing dielectric properties. A range of polyurea (PU)-based polymers are predicted from different structural unit combinations by machine learning and synthesized two representative polymers with high dielectric constants (K) and thermal stability. These polymers are combined with PI to form a twisted polymer via hydrogen bonding interactions (HNP). Both experimental results and computational simulations demonstrate the twisted structure disrupts the conjugated structure to widen the bandgap and increase dipole moment through the twisting of polar groups, leading to simultaneous improvements in both K and Eb. Consequently, HNP-20% achieves an ultrahigh Ud of 6.42 Jcm-3 with an efficiency exceeding 90% at 200 °C. This work opens a new avenue to scalable high Ud all-polymer dielectric for high-temperature applications.

Growth of L-asparagine monohydrate organic single crystals: An experimental and DFT computational approach for nonlinear optical applications

Good optical quality of L-asparagine monohydrate (C4H8N2O3.H2O) organic single crystal has been grown by adopting natural slow evaporation process at room temperature from aqueous solutions. The lattice parameters obtained by powder X-ray diffraction data revealed orthorhombic crystal system of the harvested crystal. The morphology and planes of the crystal have been identified. The molecular vibrations and functional groups have been specified by Fourier transform infrared (FTIR) spectroscopy studies. Energy dispersive X-ray (EDX) study has been availed to find out the elements constituting the crystal. Scanning electron microscopy, (SEM), provided the surface morphology of the crystal. The dependence of dielectric properties on frequency and temperature have been investigated and the electronic polarizability (α) has been determined. UV–vis spectral analysis shows that the crystal possesses good optical transmittance in the visible part of the energy spectrum. The optical band gap and the Urbach energy have been determined from lower absorption edge. Third order nonlinear susceptibility χ(3), nonlinear refractive index (n2), and linear susceptibility χ(1) have been calculated by Miller's generalized rule. The first-principle computation of band structure of electrons and the electron density of states have been discussed, which suggest that the crystals possess direct band gap. Density Functional Theory (DFT) with B3LYP function by Gaussian09W software was utilized to calculate HOMO-LUMO energy gap as well as non-linear optical parameters namely, linear polarizability (α), hyperpolarizability (β and γ) and dipole moment (μ) of L-asparagine monohydrate crystal. All the findings prove that L-asparagine monohydrate is a promising NLO crystal.

Chemical bond based machine learning model for dipole moment: Application to dielectric properties of liquid methanol and ethanol

We introduce a versatile machine-learning scheme for predicting dipole moments of molecular liquids to study dielectric properties, implemented in . We attribute the center of mass of Wannier functions, called Wannier centers, to each chemical bond and create neural network models that predict the Wannier centers for each chemical bond. Application to liquid methanol and ethanol shows that our neural network models successfully predict the dipole moment of various liquid configurations in close agreement with DFT calculations. We show that the dipole moment and dielectric constant in the liquids are greatly enhanced by the polarization of Wannier centers due to local intermolecular interactions. The calculated dielectric spectra quantitatively agree with experiments over terahertz (THz) to infrared regions. Furthermore, we investigate the physical origin of THz absorption spectra of methanol, confirming the importance of translational and librational motions. Our method is applicable to other molecular liquids and can be widely used to study their dielectric properties. Published by the American Physical Society 2024

Effect of Electric Field on Carbon Encapsulation and Catalytic Activity of Pd for Efficient Formic Acid Decomposition

Utilizing carbon coated ferroelectric materials to introduce polarization‐induced electric field (PIEF) stimulates research of electric field‐assisted catalysts for various reactions. However, effect of PIEF on carbon coating mechanism has not been studied. Herein, tourmaline nanoparticles (TNPs) with spontaneous dipole moments were applied as the PIEF supplier and sucrose was utilized as the carbon precursor to synthesize carbon coated TNPs (TNP@SC) to uncover the influence of PIEF on the carbon coating and catalytic activity of Pd toward formic acid decomposition (FAD). PIEF enhanced the adsorption capacity of TNPs for the caramelized intermediate species and increased H+ concentration by facilitating water ionization. Polymerization of adsorbed caramelized intermediate species on TNPs was accelerated. Uniformly coated carbon layer with more defects, larger specific surface area, and higher porosity was coated on TNP. Such surface properties of the carbon layer were beneficial for strongly anchoring ultrafine Pd nanoparticles. Owing to the specific properties of carbon layer and existence of PIEF, Pd/TNP@SC exhibited higher FAD activity than the catalysts absent of PIEF. Stronger PIEF leaded to higher initial turnover frequency. This study provides guidance to supply electric field for catalysis.

Immersed boundary method for dynamic simulation of polarizable colloids of arbitrary shape in explicit ion electrolytes.

We develop a computational method for modeling electrostatic interactions of arbitrarily shaped, polarizable objects on colloidal length scales, including colloids/nanoparticles, polymers, and surfactants, dispersed in explicit ion electrolytes and nonionic solvents. Our method computes the nonuniform polarization charge distribution induced in a colloidal particle by both externally applied electric fields and local electric fields arising from other charged objects in the dispersion. This leads to expressions for electrostatic energies, forces, and torques that enable efficient molecular dynamics and Brownian dynamics simulations of colloidal dispersions in electrolytes, which can be harnessed to accurately predict structural and transport properties. We describe an implementation in which colloidal particles are modeled as rigid composites of small spherical beads that tessellate the surface of the particle. The electrostatics calculations are accelerated using a spectrally accurate particle-mesh-Ewald technique implemented on a graphics processing unit and regularized such that the electrostatic calculations are well-defined even for overlapping bodies. We illustrate the effectiveness of this approach with a comprehensive set of calculations: the induced dipole moments and forces for individual, paired, and lattice configurations of spherical colloids in an electric field; the induced dipole moment and torque for anisotropic particles subjected to an electric field; the equilibrium ion distribution in the double layer surrounding charged colloids; the dynamics of charged colloids; and the behavior of ions in the double layer of a polarizable colloid under the influence of an electric field.

Effect of weak intermolecular interactions on the ionization of benzene derivatives dimers.

The interactions between π-systems in dimers of aromatic molecules lead to particularly stable conformations within the relative orientations of the monomers. Extensive research has been conducted on the properties of these complexes in the neutral state. However, in recent decades, there has been a significant surge in applications harnessing these structures for electrical purposes. Therefore, this study places particular emphasis on a deeper understanding of the redox properties of these compounds and how to modify them. To achieve this, we have focused on modeling the effect of a wide range of functional groups on the redox properties of benzene derivatives, observing a correlation between these properties and the change in the molecular dipole moment. Then, we investigated the effect of π-stacking interactions on these properties in dimers formed by either identical or different monomers. In both cases, there is an enhancement of the reducing character of the systems due to these interactions. Upon oxidation, the charge is distributed proportionally to the redox potential of each monomer. Therefore, if there is heterogeneity in these potentials, the properties of the complete cationic system will be influenced by the monomer with a greater tendency to undergo oxidation. The considered models serve as an excellent example for studying the behavior of nucleobases in DNA or aromatic amino acids, among others.