Local Field Effects Research Articles

Bipolar Membranes With Controlled, Microscale 3D Junctions Enhance the Rates of Water Dissociation and Formation

AbstractA soft lithographic method is developed for making bipolar membranes (BPMs) with catalytic junctions formed from arrays of vertically oriented microscale cylinders. The membranes are cast from reusable polydimethylsiloxane (PDMS) molds made from silicon masters, which are fabricated on 2″ to 4″ wafer scales by nanosphere lithography. High‐aspect‐ratio junctions are made on a length scale similar to the thickness of optimized catalyst layers for water dissociation, creating a platform for probing the dual effects of catalysis and local electric field at the microscale BPM junction. Optimized polymer materials and nanoscale metal oxide catalysts are used in this study. 3D BPMs are tested under reverse and forward bias conditions, exhibiting superior performance relative to their 2D counterparts. Under forward bias in H2‐O2 fuel cells, 3D BPMs achieve a current density of 1500 mA cm−2, ≈7 times higher than 2D membranes made from the same materials.

Improved piezoelectric properties and thermal stability in ZnO-modified 0.39BiScO3-0.61PbTiO3 ceramics by structure regulation

In this work, ZnO was introduced into 0.39BiScO3-0.61PbTiO3 (xZn-BS-61PT), and the phase structure and local structure of ceramics were controlled by a combination of cation substitution and ceramic/semiconductor composite, so as to improve the piezoelectric properties and temperature stability of ceramics. Zn2+ substitute B-site Ti4+ of BS-61PT, resulting in a stable coexistence of rhombohedral (R)-tetragonal (T)-monoclinic (M) phases dominated by T phase. Excessive Zn ions displace the Sc ions, making Sc ions spontaneously crystallize at grain boundaries in the form of an oxide at x ≥ 0.015. The piezoelectric coefficient and Curie temperature (d33, Tc) are increased from (326 pC/N, 416 °C) for x = 0 to (431 pC/N, 433 °C) for x= 0.015. After annealing at 200 °C, the ZnO-modified samples still retrain high d33 value (d33 > 330 pC/N). For x=0.015 sample, after aged 12 months, the retrained d33 is 395 pC/N, only down 8%. The improved properties are attributed to the synergistic effects of phase structure, point defects and local electric fields. Our results provide a design strategy to simultaneously improve the piezoelectric properties and temperature stability. Meanwhile, it is beneficial to broaden the phase.boundary (MPB) composition range of BS-xPT ceramics, and reduce the dependence of performance on components.

A study of optical properties and electron energy loss spectra of ZnS by linear response theory

The linear response theory has been applied to study the optical properties and electron energy loss spectra of ZnS. The ground state is built using the Full-Potential Linearized Augmented Plane Wave method. Thereafter, the electronic properties such as band structure and density of states are calculated. Calculations of electron energy loss spectra and optical properties are performed on the top of these ground state electronic properties. The calculations are performed using three exchange–correlation kernels namely, adiabatic local density approximation, long range contribution, and the bootstrap. The random phase approximation is also considered. An approach proposed by us to find the material dependent parameter α is used in long range contribution kernel to capture more accurate optical properties. Three values of α viz 0.78, 1.09, and 1.22 are considered. It is observed that the α = 0.78 gives very good results. This proposed scheme is found to work very well for ZnS also. The effect of local field and electron–hole interaction on the spectra is examined. For example after incorporating local field effect the high frequency dielectric constant ε∞ [i.e. ε1E→0eV ], reduces by 9.19, 12.26, 13.51 and 11.02% for random phase approximation, adiabatic local density approximation, long range contribution and bootstrap kernel respectively. In EELS plasmon peak positions are found using the three kernels and random phase approximation. A good accord with experimental results is noted after incorporating local field effects. It is observed that local field effect causes redshift of prominent peak (i.e. plasmon peak) in electron energy loss spectra by 0.61 eV.

Supercontinuum generation from silver nano species embedded sodium antimony zinc borate glass matrices

Abstract Glass composites that contain metal nanostructures exhibit improved nonlinear properties and ultrafast responses due to their inherent local field effects. In this work, we synthesized glass matrices embedded with diverse silver nano species through the ion exchange method and investigated the generation of supercontinuum from these composites. The formation of silver nano species and their volume fraction were analyzed using the XPS analysis, and their contribution towards supercontinuum broadening was studied. The size of a nanoparticle influences the electron–electron scattering and the frequency of acoustic breathing rate, which influences the extent of supercontinuum broadening. The result indicates the possibility of tuning the nonlinear response of glass nanocomposites by varying the volume fraction of Ag+ and Ag°.

Beyond the random phase approximation (RPA): First principles calculation of the valence EELS spectrum for KBr including local field, quasiparticle, excitonic and spin orbit coupling effects

The low energy region (< 50 eV) of the electron energy loss spectrum (EELS) can contain a great deal of spectral detail associated with excitations of the valence electrons. Calculation of the spectra from first principles can assist with interpretation and the most widely used method is the random phase approximation (RPA), usually neglecting local field effects (LFE). For KBr this approach is insufficient due to the importance of quasiparticle and excitonic effects. Calculations including these multi-electron effects are shown to give much improved agreement with the experimental spectra, and the inclusion of spin-orbit coupling (SOC) reproduces the excitonic doublet just above band-edge onset. A review of the complex theory behind these methods is given along with practical guidance on performing these calculations.

Frequency stabilization of adiabatic temperature change in Fe50Rh50 alloy in a cyclic magnetic field of 1.2 T

We present the results of direct measurements of the adiabatic temperature change (ΔTad) for the Fe50Rh50 alloy in a cyclic magnetic field (CMF) of 1.2 T. It is shown that increasing the frequency of the CMF from 1 to 30 Hz is accompanied by a shift of the position of temperature dependence ΔTad(T) maximum, Tmax, toward low temperatures. With an increase in the CMF frequency from 1 to 5 Hz, the ΔTmax value decreases by ∼12%. A further increase in frequency leads to stabilization of the effect. In the vicinity of the antiferromagnetic-ferromagnetic phase transition point TC = 370 K, ΔTad exhibits unconventional frequency behavior: while at T well above TC, the value of ΔTad monotonously decreases as frequency increases, at T = 370.4 K; an interval of frequency-independent ΔTad up to 10 Hz is observed, and at 368 K &amp;lt; T &amp;lt; TC, the maximum of ΔTad(f) dependence is found in the interval 1 &amp;lt; f &amp;lt; 10 Hz. Such behavior in the future can be applied in magnetic cooling technology due to large values of ΔTad and the frequency stability of the effect in alternating fields. The specific cooling power reaches giant values of ∼22 W/g at 20 Hz, which is comparable to the values under the same conditions for Gd −21.6 W/g. The unconventional behavior of ΔTad in the CMF is discussed in the context of the role of secondary phase localization, which leads to an enhanced internal local magnetic field and dynamic effects of ΔTad.

Emergence of String Monodromy in Effective Field Theory.

We demonstrate that when the field theory Kleiss-Kuijf and Bern-Carrasco-Johansson relations are imposed on one color ordering of general local bi-adjoint scalar effective field theories, the string monodromy relations must be obeyed by the other color ordering. This is a surprising example of an open string world-sheet property appearing in a purely field theoretic context. As part of the derivation, we show that nonlinear relations among the four-point Wilson coefficients arise from imposing linear symmetries on the six-point amplitude via factorization.

Sub-femtomolar vertical graphene field effect immunosensor for detection of lung tumor markers

Lung cancer is the main cancer that endangers human life worldwide, with the highest mortality rate. The detection of lung tumor markers is of great significance for the early diagnosis and subsequent treatment of lung cancer. In this study, a vertical graphene field effect transistor (VGFET) immunosensor based on graphene/C60 heterojunction was created to offer quantitative detections for the lung tumor markers carcinoembryonic antigen (CEA), cytokeratin 19 fragment (Cyfra21-1), and neuron-specific enolase (NSE). The experimental results showed that the sensitive range for standard antigen is between 1 pg/ml to 100 ng/ml, with a limit of detection (LOD) of 5.6 amol/ml for CEA, 33.3 amol/ml for Cyfra 21–1 and 12.8 amol/ml for NSE (1 pg/ml for all). The detection accuracy for these tumor markers was compared with the clinically used method for clinical patients on serum samples. Results are highly consistent with clinically used immunoassay in its efficient diagnosis concentration range. Subsequently, the mesoporous silica nanospheres (MSNs) with an average size of 90 nm were surface modified with glutaraldehyde, and a second antibody was assembled on MSNs, which fixes nanospheres on the antigen and amplified the field effect. The LODs for three markers are 100 fg/ml (0.56 amol/ml for CEA) under optimal circumstances of detection. This result indicates that specific binding to MSNs enhances local field effects and can achieve higher sensing efficiency for tumor marker detection at extremely low concentrations, providing effective assistance for the early diagnosis of lung cancer.

Hyperbolic response and low-frequency ultra-flat plasmons in inhomogeneous charge-distributed transition-metal monohalides.

Plasmon, the collective oscillations of free electron gas in materials, determines the long-wavelength excitation spectrum and optical response, are pivotal in the realm of nanophotonics and optoelectronics. In this study, using the first-principles calculations, we systematically investigated the dielectric response and plasmon properties of bulk transition-metal monohalides MXs (M = Zr, Mo; X = Cl, F). Due to the strong electronic anisotropy, MXs exhibit a broadband type-II hyperbolic response and direction-dependent plasmon modes. Particularly, local field effect (LFE) driven by the charge distribution inhomogeneity, significantly modifies the optical response and excitation spectra in MX along the out-of-plane direction. Taking into account LFE, the energy dissipation along the out-of-plane direction is almost completely suppressed, and an ultra-flat and long-lived plasmon mode with a slow group velocity is introduced. This finding reveals the role of charge density in modifying the optical response and excitation behavior, shedding light on potential applications in plasmonics.

Micromechanical modeling of discontinuous long fiber reinforced composites

The performance of discontinuous fiber composites is intricately linked to the microstructure of the composite material. Therefore, micromechanics prove valuable for the analysis and design of these materials. Two micromechanics theories, the high fidelity generalized method of cells and Carrera Unified Formulation, are used to model a repeating unit cell (RUC) of the Tailorable Universal Feedstock for Forming, a highly aligned discontinuous fiber carbon fiber composite system. The models are evaluated for their ability to predict the effective properties and local stress fields within the RUC. The stress fields between the fiber ends and the fiber-matrix interfacial stresses are of particular interest. The models are used to predict the effective properties of single fiber and multiple fiber RUCs with varying fiber-to-fiber end gap lengths, as well as the local stresses in the fiber and matrix. Both models produced similar results and demonstrated that they could capture the complex local load transfer. A statistical study is also undertaken to understand the effect of gap clustering on the effective properties and local stress fields.

Quantum Defect Sensitization via Phase-Changing Supercharged Antibody Fragments.

Quantum defects in single-walled carbon nanotubes promote exciton localization, which enables potential applications in biodevices and quantum light sources. However, the effects of local electric fields on the emissive energy states of quantum defects and how they can be controlled are unexplored. Here, we investigate quantum defect sensitization by engineering an intrinsically disordered protein to undergo a phase change at a quantum defect site. We designed a supercharged single-chain antibody fragment (scFv) to enable a full ligand-induced folding transition from an intrinsically disordered state to a compact folded state in the presence of a cytokine. The supercharged scFv was conjugated to a quantum defect to induce a substantial local electric change upon ligand binding. Employing the detection of a proinflammatory biomarker, interleukin-6, as a representative model system, supercharged scFv-coupled quantum defects exhibited robust fluorescence wavelength shifts concomitant with the protein folding transition. Quantum chemical simulations suggest that the quantum defects amplify the optical response to the localization of charges produced upon the antigen-induced folding of the proteins, which is difficult to achieve in unmodified nanotubes. These findings portend new approaches to modulate quantum defect emission for biomarker sensing and protein biophysics and to engineer proteins to modulate binding signal transduction.

Revealing Interface Polarization Effects on the Electrical Double Layer with Efficient Open Boundary Simulations under Potential Control.

A major challenge in modeling interfacial processes in electrochemical (EC) devices is performing simulations at constant potential. This requires an open-boundary description of the electrons, so that they can enter and leave the computational cell. To enable realistic modeling of EC processes under potential control we have interfaced density functional theory with the hairy probe method in the weak coupling limit (Zauchner et al. Phys. Rev. B 2018, 97, 045116). Our implementation was systematically tested using simple parallel-plate capacitor models with pristine surfaces and a single layer of adsorbed water molecules. Remarkably, our code's efficiency is comparable with a standard DFT calculation. We reveal that local field effects at the electrical double layer induced by the change of applied potential can significantly affect the energies of chemical steps in heterogeneous electrocatalysis. Our results demonstrate the importance of an explicit modeling of the applied potential in a simulation and provide an efficient tool to control this critical parameter.

Harmonic Generation up to Fifth Order from Al/Au/CuS Nanoparticle Films.

Dual heterostructures integrating noble-metal and copper chalcogenide nanoparticles have attracted a great deal of attention in nonlinear optics, because coupling of their localized surface plasmon resonances (LSPRs) substantially enhances light-matter interactions through local-field effects. Previously, enhanced cascaded third-harmonic generation was demonstrated in Au/CuS heterostructures mediated by harmonically coupled surface plasmon resonances. This suggests a promising approach for extending nonlinear enhancement to higher harmonics by adding an additional nanoparticulate material with higher-frequency harmonic resonances to the hybrid films. Here we report the first observation of enhanced cascaded fourth- and fifth-harmonic generation in Al/Au/CuS driven by coupled LSPRs at the fundamental (1050 nm), second harmonic (525 nm), and third harmonic (350 nm) of the pump frequency. An analytical model based on incoherent dipole-dipole interactions among plasmonic nanoparticles accounts for the observed enhancements. The results suggest a novel design for efficiently generating higher harmonics in resonant plasmonic structures by means of multiple sum-frequency cascades.

Qualitatively and Quantitatively Different Configurations of Nematic-Nanoparticle Mixtures.

We consider the influence of different nanoparticles or micrometre-scale colloidal objects, which we commonly refer to as particles, on liquid crystalline (LC) orientational order in essentially spatially homogeneous particle-LC mixtures. We first illustrate the effects of coupling a single particle with the surrounding nematic molecular field. A particle could either act as a "dilution", i.e., weakly distorting local effective orientational field, or as a source of strong distortions. In the strong anchoring limit, particles could effectively act as topological point defects, whose topological charge q depends on particle topology. The most common particles exhibit spherical topology and consequently act as q = 1 monopoles. Depending on the particle's geometry, these effective monopoles could locally induce either point-like or line-like defects in the surrounding LC host so that the total topological charge of the system equals zero. The resulting system's configuration is topologically equivalent to a crystal-like array of monopole defects with alternating topological charges. Such configurations could be trapped in metastable or stable configurations, where the history of the sample determines a configuration selection.

Magnetic Domain Wall Networked Films – Configurational Switching for Tunable Magnetization Dynamics by Perforated Thin Films

AbstractSetting the magnetization and its properties in magnetic materials and films is of the utmost fundamental and technological importance for magnetic applications and devices. Magnetic permeabilities in a material are generally defined by the acting magnetic anisotropies together with an applied magnetic field. Here, deterministic switching of the effective dynamic magnetic properties is demonstrated by tunable networks of magnetic domain walls. By perforating magnetic films, a reversible switching between different magnetization states is achieved. Due to the resulting local effective dynamic fields for the changed domain configurations, different zero‐field permeability spectra are attained for the same material structure. Using local configurational magnetic resonances confined by magnetic domain walls, deterministic switchable bimodal dynamic behavior is achieved. Dynamic magnetooptical Kerr microscopy with picosecond temporal resolution proves that the varying periodic magnetic domain configurations are responsible for the dynamic magnetic bistability. In particular, the field‐free precessional magnetic response can be reproducibly switched between 1.3 and 2.3 GHz. The magnetization dynamics can be modified by small interventions in a repeatable manner beyond fixed material and structural properties. The described fundamental mechanism enables to design new energy efficient configurational microwave devices by switching between zero‐field magnetic arrangements.

Catalytic divergencies in the mechanism of L-arginine hydroxylating nonheme iron enzymes.

Many enzymes in nature utilize a free arginine (L-Arg) amino acid to initiate the biosynthesis of natural products. Examples include nitric oxide synthases, which generate NO from L-Arg for blood pressure control, and various arginine hydroxylases involved in antibiotic biosynthesis. Among the groups of arginine hydroxylases, several enzymes utilize a nonheme iron(II) active site and let L-Arg react with dioxygen and α-ketoglutarate to perform either C3-hydroxylation, C4-hydroxylation, C5-hydroxylation, or C4-C5-desaturation. How these seemingly similar enzymes can react with high specificity and selectivity to form different products remains unknown. Over the past few years, our groups have investigated the mechanisms of L-Arg-activating nonheme iron dioxygenases, including the viomycin biosynthesis enzyme VioC, the naphthyridinomycin biosynthesis enzyme NapI, and the streptothricin biosynthesis enzyme OrfP, using computational approaches and applied molecular dynamics, quantum mechanics on cluster models, and quantum mechanics/molecular mechanics (QM/MM) approaches. These studies not only highlight the differences in substrate and oxidant binding and positioning but also emphasize on electronic and electrostatic differences in the substrate-binding pockets of the enzymes. In particular, due to charge differences in the active site structures, there are changes in the local electric field and electric dipole moment orientations that either strengthen or weaken specific substrate C-H bonds. The local field effects, therefore, influence and guide reaction selectivity and specificity and give the enzymes their unique reactivity patterns. Computational work using either QM/MM or density functional theory (DFT) on cluster models can provide valuable insights into catalytic reaction mechanisms and produce accurate and reliable data that can be used to engineer proteins and synthetic catalysts to perform novel reaction pathways.

Intrinsic high frequency permeability of magnetic nanocomposites: uncertainty principle

The intrinsic high frequency permeability spectra of ferromagnetic conductive nanocomposites containing different volume fractions of nanoscale iron and cobalt have been simulated. A law is proposed to explain the simulated results by assuming that there are plenty of Landau–Lifshitz–Gilbert (LLG) type natural resonances contributing to the intrinsic permeability spectra. The results clearly show that the spectra strongly depend on the distribution of local effective magnetic field, the interaction between the magnetic particles, the inhomogeneous damping constant of LLG precession, and the initial equilibrium states. Especially, the effect of particles shape distribution in each sampling on the local effective magnetic field. In view of this fact: it is absolutely impossible to have the same effect from these factors when someone prepares several measurement samples, an uncertainty principle is believed to hold for measuring the intrinsic permeability of an electromagnetic (EM) composite. Therefore, this law tells us that it should be cautious when comparing or evaluating the EM properties of composites (for instance, EM wave absorbing composites). Memory effect can be used to restore the intrinsic high frequency permeability for a specific defunct composite sample.

Modeling the near-field effect on molecular excited states using the discrete interaction model/quantum mechanical method.

Strong light-matter interactions significantly modify the optical properties of molecules in the vicinity of plasmonic metal nanoparticles. Since the dimension of the plasmonic cavity approaches that of the molecules, it is critical to explicitly describe the nanoparticle junctions. In this work, we use the discrete interaction model/quantum mechanical (DIM/QM) method to model the coupling between the plasmonic near-field and molecular excited states. DIM/QM is a combined electrodynamics/quantum mechanical model that uses an atomistic description of the nanoparticle. We extend the DIM/QM method to include the local field effects in the sum-over-state formalism of time-dependent density functional theory. As a test of the method, we study the interactions between small organic chromophores and metal nanoparticles. In particular, we examine how the inclusion of multiple electronic transitions and intermolecular interactions modify the coupling between molecules and nanoparticles. Using the sum-over-state formalism of DIM/QM, we show that two-state models break down when the plasmon excitation is detuned from the molecular excitations. To gain further insight, we compare the simple coupled-dipole model (CDM) with the DIM/QM model. We find that CDM works well for simple systems but fails when going beyond the single molecule or single nanoparticle cases. We also find that the coupling depends strongly on the site of the nanoparticle in which the chromophore couples to. Our work suggests the importance of explicitly describing the cavity to capture the atomistic level local field environment in which the molecule strongly couples to.

Gold Nanorods - An Overview

This article provides an overview of current research in structure, synthesis, properties, application of gold nanorods. Interest in rod- shaped nanoparticles steam of unique optical properties, A gold nanorod is defined as nanometer-sized gold particles that are rod shaped. These solid, cylindrical nanoparticles have uniform diameters ranging from a few nanometers to hundreds of nanometers, with aspect ratios (length/diameter) larger than 1 but typically smaller than 10. The most popular and successful method for creating high-quality gold nanorods is seed-mediated development. optical properties of gold nanorods, absorption spectrum of colloidal dispersion of gold nanorods, local field effect and sensing application, color of colloidal dispersion of gold nanorod, polarization dependent color and absorption in polymer gold. Gold nanorods are utilized in a range of applications including biosensing, photothermal therapy, bioassays, biomedical imaging, and drug delivery. All these properties make gold nanorod a good candidate for future nanoelectronics in this article, we will describe the preparation and characterization of gold nanorods.

Negative differential resistors from carbon-based cryogels incorporating graphene oxide into a ferroelectric polymer matrix

Electronic components with negative differential resistance (NDR) are essential in power electronics to build Gunn diodes, varactors, parametric amplifiers and switching circuits. However, their implementation through silicon-based electronics is costly and demands complex circuitry and components. Here, we introduce for the first time a class of hybrid carbon-based and organic aerogels, prepared at liquid nitrogen temperature (77 K) by a simple and scalable freeze-drying method. These cryogels exhibit NDR. In these cryogels, the carbonaceous phase is represented by d-glucose-graphene oxide nanocomposites while the organic phase is represented by polyvinylidene difluoride (PVDF), a ferroelectric polymer. NDR in our samples is assigned to the local electric field effects of PVDF on the charge carriers of more electrically conducting graphene oxide and d-glucose. Through an operando study via scanning near-field optical microscopy, we also show that low thermal expansion and low thermal conductivity are essential to prevent undesired effects in our devices through parasitic capacitance's discharge.