Electron Density Research Articles

Ambiguities in Decomposing Molecular Polarizability into Atomic Charge Flow and Induced Dipole Contributions.

The molecular dipole polarizability can be decomposed into components corresponding to the charge flow between atoms and changes in atomic dipole moments. Such decompositions are recognized to depend on how atoms are defined within a molecule, as, for example, by Hirshfeld, iterative Stockholder, or quantum topology partitioning of the electron density. For some of these, however, there are significant differences between the numerical results obtained by analytical response methods and finite field calculations. We show that this difference is due to analytical response methods accounting for (only) the change in electron density by a perturbation, while finite field methods may also include a component corresponding to a perturbation-dependent change in the definition of an atom within a molecule. For some atom-in-molecule definitions, such as the iterative Hirshfeld, iterative Stockholder, and quantum topology methods, the latter effect significantly increases the charge flow component. The decomposition of molecular polarizability into atomic charge flow and induced dipole components thus depends on whether the atom-in-molecule definition is taken to be perturbation-dependent.

2,4-dichloro-6-(1,4,5-triphenyl-1H-imidazol-2-yl) phenol: synthesis, DFT analysis, Molecular docking, molecular dynamics, ADMET properties against COVID-19 main protease (Mpro: 6WCF/6Y84/6LU7)

ABSTRACT New derivatives of 2,4-dichloro-6-(1,4,5-triphenyl-1H-imidazol-2-yl) phenol (DPIP) have been successfully synthesised and characterised using spectral methods such as FT-IR, 1H NMR and 13C NMR. Density functional theory (DFT) approach at B3LYP/6-311 G (d, p) level of theory is used to determine optimised bond parameters and single crystal XRD investigation of related derivatives confirms the structure of DPIP bond parameters. The single crystal XRD measurements and the optimised geometrical parameters produced by the DFT calculation agree well. The FT-IR bands seen in the experiment were attributed to distinct normal modes of the molecule. Frontier molecular orbital computations described the molecule stability, chemical reactivity and charge transfer. Atomic charges determined via Mulliken population analysis on the different DPIP atoms. MEP, which is mapped to the electron density surfaces, has discovered potential reactive sites of the molecule. The reported molecule is used as a potential NLO material since it has a high μβ0 value. Binding affinities were discovered using molecular docking against the COVID-19 major protease (Mpro: 6WCF/6Y84/6LU7). The behaviour of the complex structure formed by the Covid-19 protein under in silico physiological conditions was then confirmed by a 100 ns molecular dynamic simulation which looked at the structure stability over time and revealed a stable conformation and binding pattern in an environment of imidazole derivatives. Furthermore, favourable to moderate anti-viral activity was revealed by an in-silico analysis that anticipated the compound absorption, distribution, metabolism, excretion and toxicity profiles (ADMET).

The electron density at the midpoint of the plasmapause

The high density plasmasphere in the magnetosphere is often separated from a lower density region outside of the plasmasphere, called the plasmatrough, by a sharp gradient in electron density called the plasmapause. Here we use plasmapause events identified from electron density data from the ISEE, CRRES, Polar, and IMAGE missions, and the nonlinear genetic algorithm TuringBot, to find models for the electron density at the midpoint of the plasmapause, ne,pp. A good model for ne,pp should include dependence on L, which is the strongest dependence. But models can be improved by including weaker dependencies on the magnetic local time, MLT, the solar EUV index F10.7, and geomagnetic activity as indicated by averages of Kp and AE. The most complicated model that we present predicts ne,pp within a factor of 1.64, and is within the range of observed plasmapause densities for about 96% of our events. These models can be useful for separating plasma populations into plasmasphere-like and plasmatrough-like populations. We also make available our database of electron density measurements categorized into various populations.

Influence of the electron density on the giant negative magnetoresistance in two-dimensional electron gases

variation of the electron density via a metallic gate can control the disorder potentials in two-dimensional electron gases (2DEGs). This also influences the negative magnetoresistance at low magnetic fields, which is commonly observed in ultrahigh mobility 2DEGs. We investigate the temperature-dependent giant negative magnetoresistance (GNMR) as a function of the electron density for several temperatures and currents. Thereby, we find that the GNMR behavior depends decisively on the electron density. This observation is attributed to a changed disorder potential with electron density. In the case of higher electron densities, a nonlinear current dependency of the GNMR is observed, which could be described within the hydrodynamic regime. Published by the American Physical Society 2024

Density functional theory beyond the Born–Oppenheimer approximation: exact mapping onto an electronically non-interacting Kohn–Sham molecule

This work presents an alternative, general, and in-principle exact extension of electronic Kohn–Sham density functional theory (KS-DFT) to the fully quantum-mechanical molecular problem. Unlike in existing multi-component or exact-factorization-based DFTs of electrons and nuclei, both nuclear and electronic densities are mapped onto a fictitious electronically non-interacting molecule (referred to as KS molecule), where the electrons still interact with the nuclei. Moreover, in the present molecular KS-DFT, no assumption is made about the mathematical form (exactly factorized or not) of the molecular wavefunction. By expanding the KS molecular wavefunction à la Born–Huang, we obtain a self-consistent set of ‘KS beyond Born–Oppenheimer’ electronic equations coupled to nuclear equations that describe nuclei interacting among themselves and with non-interacting electrons. An exact adiabatic connection formula is derived for the Hartree-exchange-correlation energy of the electrons within the molecule and, on that basis, a practical adiabatic density-functional approximation is proposed and discussed.

Properties of the ionization region in a magnetron plasma at gas-aggregation-source-relevant pressure regime explored using a global model

Abstract A global (volume averaged) model is developed for the ionization region of a gas aggregation source (GAS) plasma. The case of using argon gas and a copper target is considered. The model describes the densities of thermal and hot electrons, argon and copper ions, copper atoms and argon atoms in different excited states, the temperature of thermal electrons, the kinetic energies of the ions with which they bombard the target, the sheath width near the target cathode and the energy fluxes by different plasma species to a planar probe in the ionization region. Also, the fraction of input power is estimated which is dissipated to energize the thermal electrons in the ionization region. The gas discharge properties are analysed for different pressures and discharge currents under conditions corresponding to the experimental conditions (Gauter S et al 2018 J. Appl. Phys. 124 073301). The calculated pressure- and current-dependences for the GAS properties are used to explain the measured dependences for the deposition rate and the energy flux. It is found that the deposition rate increases with increasing discharge current because of the growth of currents of copper atoms and ions. With increasing pressure, the rate decreases due to drop of the densities of copper atoms and ions because of decreasing the kinetic energies of the ions with which they bombard the target. The model indicates that in the gas-aggregation-source relevant pressure regime, the energy flux by ions dominates over the energy fluxes of other plasma species.

Double Superconducting Dome of Quasi Two-Dimensional TaS2 in Non-Centrosymmetric van der Waals Heterostructure.

Two-dimensional van der Waals heterostructures (2D-vdWHs) based on transition metal dichalcogenides (TMDs) provide unparalleled control over electronic properties. However, the interlayer coupling is challenged by the interfacial misalignment and defects, which hinders a comprehensive understanding of the intertwined electronic orders, especially superconductivity and charge density wave (CDW). Here, by using pressure to regulate the interlayer coupling of non-centrosymmetric 6R-TaS2 vdWHs, we observe an unprecedented phase diagram in TMDs. This phase diagram encompasses successive suppression of the original CDW states from alternating H-layer and T-layer configurations, the emergence and disappearance of a new CDW-like state, and a double superconducting dome induced by different interlayer coupling effects. These results not only illuminate the crucial role of interlayer coupling in shaping the complex phase diagram of TMD systems but also pave a new avenue for the creation of a novel family of bulk heterostructures with customized 2D properties.

On the perturbation of the interferometric phase in interferometry-polarimetry of fusion plasmas

The perturbation of the interferometric phase is a corrective term of the measured phase shift that should be taken into account in the measurement of the electron line density in a combined interferometer-polarimeter for the diagnostics of the electron density and the magnetic field in a fusion plasma. In this paper we first review in detail the theory of this effect and present a new and complete derivation of it, which also accounts for some errors published in a previous paper. Then we consider this effect in the interferometer-polarimeter of three different plasma devices: RTP, JET and DTT and for each machine we calculate the expected phase perturbation for a typical plasma profile, especially with reference to the use of the popular three-wave technique for the polarization modulation of the input probing beam.

Plasma electron acceleration driven by a long-wave-infrared laser

Laser-driven plasma accelerators provide tabletop sources of relativistic electron bunches and femtosecond x-ray pulses, but usually require petawatt-class solid-state-laser pulses of wavelength λL ~ 1 μm. Longer-λL lasers can potentially accelerate higher-quality bunches, since they require less power to drive larger wakes in less dense plasma. Here, we report on a self-injecting plasma accelerator driven by a long-wave-infrared laser: a chirped-pulse-amplified CO2 laser (λL ≈ 10 μm). Through optical scattering experiments, we observed wakes that 4-ps CO2 pulses with < 1/2 terawatt (TW) peak power drove in hydrogen plasma of electron density down to 4 × 1017 cm−3 (1/100 atmospheric density) via a self-modulation (SM) instability. Shorter, more powerful CO2 pulses drove wakes in plasma down to 3 × 1016 cm−3 that captured and accelerated plasma electrons to relativistic energy. Collimated quasi-monoenergetic features in the electron output marked the onset of a transition from SM to bubble-regime acceleration, portending future higher-quality accelerators driven by yet shorter, more powerful pulses.

Electronic Delocalization Engineering of β‐AsP Enabled High‐Efficient Multisource Logic Nanodevices

AbstractDelocalized electron and phonon structures are directives for rationally tuning the intrinsic physicochemical properties of 2D materials by redistributing electronic density. However, it is still challenging to accurately manipulate the delocalized electron and systematically study the relationships between physiochemical properties and practical nanodevices. Herein, the effects of delocalized electrons engineering on blue‐arsenic‐phosphorus (β‐AsP)‐based practical devices are systematically investigated via implementing vacancies or heteroatom doping. A tendency of carrier conductivity property from “half‐metal” to “metal” is initially found when tuning the electronic structure of β‐AsP with adjustable vacancy concentrations below 2 at% or above 3 at%, which can be ascribed to the introduction of delocalized electrons that cause asymmetric contributions to the electronic states near the implementation site. In optical logic device simulations, broadband response, triangular wave circuit system signal, and reverse polarization anisotropy are achieved by adjusting the vacancy concentration, while extinction ratios are as high as 1561. The electric and thermic‐logic devices realize the highest available reported giant magnetoresistance (MR) up to 1013% and 1039% at vacancy concentrations of 1.67% and 0.89%, respectively, which is significantly superior to the reports. The results shed light on the electronic delocalization strategy of regulating internal structures to achieve highly efficient nanodevices.

Bifunctional Strontium Cobalt Molybdenum Oxide (Sr2CoMoO6) Perovskite as an Efficient Catalyst for Electrochemical Water Splitting Reactions in Alkaline Media

Developing earth‐abundant low‐cost electrocatalysts is of prime research interest towards the need for clean energy technology, such as water‐splitting reactions. Herein, we have explored the electrocatalytic activity of the double perovskite‐based strontium cobalt molybdenum oxide (SCMO) towards water‐splitting reactions, both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Prepared by scalable autocombustion synthesis, the as‐synthesised bulk SCMO perovskite exhibited impressive electrocatalytic performance attributed to its substantial electrochemical active surface area. For the OER, it exhibited an overpotential of 350 mV with a Tafel slope value of 76 mV/dec. Concurrently, it showed proficient activity in the HER, revealing an overpotential of 270 mV and a Tafel slope of 112 mV/dec. Further, this perovskite material was stable during continuous electrocatalysis over a 24 h period with a negligible increase in observed overpotential value. The electronic density of states confirmed that the Co plays a pivotal role in enhancing electrocatalytic activities. This is achieved by a substantial reduction in the band gap and enhancement of the d‐band centre to an optimal level, rendering the system more favourable for electrocatalytic reactions. Our study contributes insights to the advancement of the design and utilization of perovskite‐based catalysts in the realm of sustainable energy technologies.

Effect of O2/n-C5H12 Ratio on Oxygenates Production from Plasma N-pentane Partial Oxidation

Objective: Non-thermal plasma is a promising method for producing clean fuels. This work provides a deeper understanding of the impact of O2/n-C5H12 ratio on the partial oxidation of n-pentane from both physical and chemical perspectives. Moreover, this work offers insight into improving fuel combustion efficiency and technical support for the preparation of clean fuels. Methods: An experimental system based on dielectric barrier discharge plasma was established. The discharge characteristics and product generation status of n-pentane partial oxidation were measured by changing the concentration of oxygen and n-pentane to evaluate different O2/n-C5H12 ratios. Results: Research on discharge characteristics showed that the O2/n-C5H12 ratio did not affect the discharge mode, and typical Lissajous shapes were present at different ratios. Changing the O2/n-C5H12 ratio affected the oxygen concentration, average electron energy or electron density, and background temperature. As the O2/n-C5H12 ratio increased, the conversion of the n-pentane partial oxidation reaction increased. However, changing the O2/n-C5H12 ratio did not affect the type of generated products. The oxygenates exhibited a volcano curve, and an O2/n-C5H12 ratio of 1.00 achieved the highest selectivity of 35.1%. As the O2/n-C5H12 ratio continued to increase, the selectivity of oxygenates decreased and the selectivity of CO2 increased. This was potentially due to a shift from partial oxidation toward complete oxidation, which led to the generation of secondary pollutants. Thus, higher O2/n-C5H12 ratios were not conducive to clean fuel production and environmental friendliness. Conclusion: In the partial oxidation of n-pentane, the highest clean fuel production rate was achieved when the O2/n-C5H12 ratio was 1.00. When this ratio exceeded 1.00, the reaction shifted toward complete oxidation, producing secondary pollutants. This study provides ideas for improving fuel combustion efficiency and technical support for the preparation of clean fuels.

Highly efficient degradation and detoxification of antibiotics over C–Dots/siderite heteroaggregates in photo-Fenton systems: The crucial role of C–Dots

The substantial presence of antibiotics in aquatic environments remains as a critical environmental issue that needs to be urgently addressed. In this study, mimetics of C–Dots/siderite heteroaggregates (CSI) were studied in a visible-light-responsive Fenton system as a platform for the degradation of antibiotics in contaminated water. By virtue of the excellent electron transfer of C–Dots, the sustained conversion cycles of Fe(II) → Fe(III) → Fe(II) in CSI were greatly accelerated, and meanwhile the H2O2 utilization was enhanced. The optimized CSI–3 nanocomposite displayed a prominent degradation efficiency towards a series of tetracycline analogs at ppb levels. Density functional theory (DFT) calculations indicated the excellent photo-Fenton catalytic performance of CSI originated from the increased d-band center and electron density, which considerably improves the utilization of H2O2. Both experimental and theoretical studies revealed that the correlated toxicity of degradation intermediates was significantly decreased. Additionally, a continuous flow device integrating the CSI photo-Fenton system maintained a high degradation efficiency after long-term treatment of simulated chlortetracycline wastewater. The presented work thereby confirms a spontaneous remediation process for the decontamination and detoxification of persistent organic pollutants under the action of heteroaggregates formed by engineered nanoparticles and natural minerals.

Non-uniformity of fluctuation characteristics inside an edge magnetic island in Heliotron J

Abstract Non-uniform fluctuation characteristics are observed within an edge magnetic island in Heliotron J. The island possesses a long connection length comparable to the confined region. These fluctuations are measured using a Langmuir probe. The island’s presence is confirmed through the plasma response, observed in the modulation amplitude of electron temperature and its phase delay relative to the heat source in a heat modulation experiment. Within the island, the electron density is notably high, accompanied by distinct profiles of electron temperature and electric field, likely attributable to the magnetic island. Contrary to expectations, density fluctuations within the edge magnetic island are not locally minimized, despite the reduced gradient of the profile within the island. Statistical analysis shows a suppression of intermittent transport inside the island, while intermittent fluctuations increase towards the exterior. A further analysis to segregate turbulence-driving and spreading factors reveals that both turbulence-driven and spreading contributions are comparably significant inside the island. Additionally, the non-uniform turbulence results in a spatially structured fluctuation-driven particle flux. Overall, the experimental findings indicate that fluctuation characteristics exhibit notable non-uniformity both inside and near the island. This non-uniformity potentially complicates heat transport and may lead to three-dimensional, asymmetric transport within and at the periphery of the islands.&amp;#xD;

Exploring the effects of a one-dimensional periodic potential on a three-dimensional topological insulator

High mobility two-dimensional systems with superposed 1D lateral periodic potentials exhibit characteristic commensurability (Weiss) oscillations that reflect the interplay of the cyclotron radius at the Fermi level and the superlattice period. Here, we impose a one-dimensional periodic potential on strained HgTe, which is a strong 3D topological insulator. By tuning the Fermi level with top gates, the effects of the artificial potential can be studied in the bulk gap, where only Dirac surface states exist, in the conduction band, and in the valence band, where Dirac electrons and holes coexist. On the electron side, we observe clear commensurability oscillations whose period is governed by the carrier density of the top-surface Dirac electrons. Unexpectedly, weak commensurability oscillations are also observed in the valence band with a period that depends on both electron and hole density. Published by the American Physical Society 2024

Hydrogen evolution descriptors of 55-atom PtNi nanoclusters and interaction with graphite

Density functional simulations have been performed for Pt n Ni 55−n clusters ( n=0,12,20,28,42,55 ) to investigate their catalytic properties for the hydrogen evolution reaction (HER). Starting from the icosahedral Pt12Ni43 , hydrogen adsorption energetics and electronic d-band descriptors indicate HER activity comparable to that of pure Pt55 (distorted reduced core structure). The PtNi clusters accommodate a large number of adsorbed hydrogen before reaching a saturated coverage, corresponding to 3–4 H atoms per icosahedron facet (in total ∼70–80). The differential adsorption free energies are well within the window of |ΔGH|<0.1 eV which is considered optimal for HER. The electronic descriptors show similarities with the platinum d-band, although the uncovered PtNi clusters are magnetic. Increasing hydrogen coverage suppresses magnetism and depletes electron density, resulting in expansion of the PtNi clusters. For a single H atom, the adsorption free energy varies between −0.32 ( Pt12Ni43 ) and −0.59 eV ( Pt55 ). The most stable adsorption site is Pt–Pt bridge for Pt-rich compositions and a hollow site surrounded by three Ni for Pt-poor compositions. A hydrogen molecule dissociates spontaneously on the Pt-rich clusters. The above HER activity predictions can be extended to PtNi on carbon support as the interaction with a graphite model structure (w/o vacancy defect) results in minor changes in the cluster properties only. The cluster-surface interaction is the strongest for Pt55 due to its large facing facet and associated van der Waals forces.

Investigating the Effects of Urea-Zinc Sulfate-L Phenylalanine on the Corrosion Inhibition of Mild Steel Exposed to pH-4 Sulfuric Acid

Background: Corrosion of mild steel is a risk to material and stability. The practice of corrosion inhibitors is a cost-effective corrosion modification method for mild steel. Organic inhibitors rich in electrons might have an excellent ability to prevent corrosion. This study aims to assess the inhibitory effect of the mixture of Urea, Zinc Sulfate, and L-Phenylalanine, which has a high electron density Methods: MS corrosion was experimentally performed using H2SO4 at a pH of 4. Different gravimetric and conventional techniques, such as polarization, AC impedance AFM, UV, and fluorescence, were used to examine the studied data. Results: According to gravimetric measurements, this combination produced 93% effective inhibition. The findings of the impedance test proved that the mixture of inhibitors that was adsorbed on the metal surface effectively prevented corrosion. Conclusion: Likewise, according to the Polarization measurements, the inhibitor exhibits mixed-type performance with significant cathodic activity. UV, Fluorescence, and AFM findings showed that MS corrosion was suppressed because the inhibitor molecule adhered to the metal's surface and reduced.

The Signature of Sporadic E of an Equatorial Ionosphere of the Low Latitude Region

Sporadic E is usually referred to as the large unpredictable formation of regions of very high electron density in the E region as one of the anomalies that is present in the equatorial region. This work studies the variability of sporadic E in the region with respect to the propagation of low frequency communication and impact on the equatorial region during the occurrence of this anomaly. Hourly data for the year 2010, a year of low solar activity obtained in-situ from a Digisonde Portable Sounder (DPS-4) from the African sector, Ilorin, Nigeria (8.5oN, 4.5oE, -2.96 dip) and the Southern American sector online at Jicamarca, Peru (12 oS, 76.8 oW, 0.74 dip) and Fortaleza, Brazil (3 oS, 38 oW, -7.03dip) were used for this study. The result obtained shows that sporadic E is usually observed at the region during the daytime and early evening (0600- 1700 local time) and is more prevalent during solstice months. Two types of sporadic E were observed in the region: blanket and transparent sporadic E. 12% of the transparent sporadic E was observed during the March equinox while 9% of blanket sporadic E was observed during this period; September equinox shows 15% of transparent and 7% blanket sporadic E respectively, while June solstice has 21% transparent and 7% blanket sporadic E. During the December solstices, 14% transparent and 7% blanket sporadic E was observed. During the March equinox, the blanket sporadic E was observed around 0200 hour local time, and that of the transparent sporadic E at about 1000 hour local time. Observation during the September equinox shows that it occurs around 1100 hour and 0200 hour respectively. It was observed that there is no correlation between sporadic E and geomagnetic storm. Sporadic E has been observed to be one of the anomalies that are responsible for the scintillation and scattering of the lower frequency signal in the said region when present.

Synthesis and Gamma-ray Shielding Efficiency of Borosilicate Glasses Doped with Zinc Oxide: Comparative Study

AbstractThis study examined the suitability of several glass compositions as a gamma-ray shielding substance. The compositions tested were of varying ZnO concentrations, specifically (60-x) B2O3—10Na2O—15SiO2—5Al2O3—(x + 10)ZnO (where X = 5, 10, 15 and 20 mol%). Measurements were performed at energy levels of 0.6642, 1.1776, and 1.3343 MeV radiated from Cs137 and Co60 point sources along with a scintillation detector [NaI(TL)]. We investigated the critical properties related to gamma radiation shielding, determining the effective atomic number (Zeff), electron density (Nel), half-value layer (HVL), linear attenuation (μ) and mass attenuation (μm) coefficients, and mean free path (λ). Our results show that the glasses under examination get denser (from 2.12 to 2.77 g/cm3) as the Zn concentration rises from 15 to 35 mol %. In addition, all glass compositions provide adequate protection against gamma radiation at the specified energy levels. The values of µ went up from 0.157 to 0.214 cm−1 (0.6642 MeV), from 0.119 to 0.160 cm−1 (1.1776 MeV), and from 0.114 to 0.151 (1.3343 MeV). For samples B1 and B4, the observed HVL values dropped from 4.41, 5.84, and 6.12 cm to 3.21, 4.31, and 4.61 cm at 0.6642, 1.1736, and 1.3343 MeV, respectively. Among the materials tested, prepared glasses show higher shielding capacity compared to regularly used glass and concrete samples. The study highlights these glass compositions' potential as practical materials that can shield gamma radiation.

RFX-mod2 diagnostic capability enhancements for the exploration of multi-magnetic-configurations

Abstract The RFX-mod2 device, the upgraded version of the previous RFX-mod with a modified magnetic boundary, is presently under realization and will start to be operated in 2025. Significant upgrades of the diagnostic capabilities have been proposed and are under development. These include a largely increased number of in-vessel magnetic and electrostatic sensors, a new fast reciprocating manipulator for the exploration of the edge plasma in a wide range of experimental conditions, the improved Thomson scattering and soft X-ray diagnostics system for a detailed determination of the behavior of the electron temperature profile, new dedicated systems for the space and time resolved analysis of X-ray spectra and neutron rate, a reflectometric diagnostic for real-time determination of plasma position, two diagnostics devoted to the imaging of light impurities and influxes behavior along with arrays of halo current sensors. These diagnostic upgrades will be accompanied by a significant effort to improve the control of the electron density and of the impurity influxes by means of proper treatment of plasma facing components with in-vessel fixed electrodes distributed over the first wall. The described advancements will allow a deeper understanding of physics phenomena in the wide variety of magnetic configurations, including the tokamak, the reversed-field pinch and the Ultra-low q, which can be produced in RFX-mod2 thanks to its flexibility and unique MHD control capabilities.