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The kinetic energy density of electrons and the gradient of the electron density have pronounced jump discontinuities at the positions of the atomic nuclei in molecules. Certain exact relations then imply that molecular Kohn–Sham exchange–correlation potentials may also be discontinuous at atomic nuclei. Here, we confirm that exchange–correlation potentials derived from Hartree–Fock and correlated wavefunctions within Slater-type basis sets do exhibit such discontinuities. Despite their persistence even in large basis sets, these discontinuities are almost certainly artifacts of basis set finiteness and are expected to disappear in the basis-set limit. The findings imply that imposing electron–nucleus cusp conditions in spherically averaged form may not always be appropriate. [ABSTRACT FROM AUTHOR]

We study the magneto-optical properties of Dirac semimetal (DSM) slabs with particular emphasis on Cd 3 As 2 through electron–photon–phonon interactions, focusing on the magneto-optical absorption coefficient (MOAC) and full-width at half maximum (FWHM). Studying the Landau level (LL) energy of DSMs in the (x y) plane and the z -direction revealed a unique deviation from the square root dependence on the magnetic field, distinguishing DSMs from other semiconductors. At high magnetic fields, the electron–hole symmetry in the LL spectrum is broken, indicating a topological phase in DSMs. For undoped DSMs, MOAC is driven by interband transitions, with peaks from one-photon absorption being smaller and positioned to the left of two-photon ones. Increasing the magnetic field increases peak values. FWHM for one- and two-photon processes increases with the magnetic field and follows a T dependence on temperature. In doped DSMs, both intraband and interband transitions occur, with new interband peaks emerging at higher temperatures near the Fermi energy. Increased electron density shifts the peak position slightly toward higher energy. Peaks from optical phonon emission are consistently higher and located to the right of those from optical phonon absorption, indicating a stronger emission process. The FWHM data allow for the estimation of electron mobilities, and using a reasonable broadening parameter, our predicted mobility values agree with experimental results. [ABSTRACT FROM AUTHOR]

Magnetically shielded Hall effect thrusters suffer from pole erosion as their life-limiting mechanism. However, the dominant physical mechanism causing this erosion remains unclear, limiting the ability create designs that mitigate erosion and the predictive accuracy of simulations used to aid in design. This paper provides spatially resolved laser Thomson scattering measurements of electron temperature and density in the near field plume of a magnetically shielded Hall effect thruster, traversing the front pole region from the discharge channel centerline to the cathode centerline. The signals are inverted in a Bayesian framework, and the data are compared qualitatively and quantitatively to simulations of the same Hall effect thruster. Based on the electron momentum equation, electron pressure gradient is used as a proxy for the electron-predicted electrostatic potential gradient. To within the accuracy of this approximation, the electron pressure has a minimum immediately in front of the front pole. Hence, ions have an electrostatic potential avenue from the discharge region to the front pole, validating this mechanism of pole erosion. [ABSTRACT FROM AUTHOR]

Noninvasive measurements of electron properties in a Hall effect thruster (HET) are needed to understand the physical processes in the acceleration region and to validate simulations. This paper presents spatially resolved laser Thomson scattering (LTS) measurements across the entire acceleration region of a HET. The test article is the H9, a 9 kW class magnetically shielded HET. The H9 is operated on krypton at a facility pressure of 1.2 × 10−5 Torr Kr (1.6 mPa). The thruster is operated at three discharge conditions: 171 V, 35 A, an inner coil current (Iic) of 4.11 A, and an outer coil current (Ioc) of 2.27 A as the baseline 6 kW condition; 154 V, 34.8 A, an Iic of 4.11 A, and an Ioc of 2.27 A to vary the discharge voltage; and 171 V, 34.4 A, an Iic of 4.52 A, and an Ioc of 2.5 A to vary the magnetic field strength. At each discharge condition, we measured axial profiles of electron density and electron temperature along the channel centerline from 5% to 95% of a channel length downstream of the channel exit plane. At the baseline condition, we also measure the axial profile of the azimuthal electron drift velocity. We measure a minimum electron density of 1.3 × 1017 m−3, peak electron temperatures around 40 eV, and a peak azimuthal electron drift velocity around 680 km/s. The results suggest the presence of anomalous electron heating and demonstrate that low discharge voltages allow LTS to access the entire acceleration region of a HET. [ABSTRACT FROM AUTHOR]

The target surface to be treated in reality is often not smooth and horizontal and may also be in different tilting angles. The treatment of the tilted dielectric surface by the atmospheric pressure plasma jet (APPJ) undoubtedly increases the complexity of surface modification. Therefore, a two-dimensional fluid model is established to reveal the internal mechanism of the interaction between the He APPJ and the tilted dielectric surface by means of numerical simulation. The distribution of the gas flow in a small angular range (0°, 3°, 5°, 8°, 10°, and 15°) is studied. In addition, the effects of the tilt angle on the jet morphology, discharge dynamic properties, and species distribution of the He APPJ are emphatically discussed. It is found that the jet morphology and parameters are no longer symmetrical under the tilted surface. With the increase in the tilt angle, the enhanced electric field in the upper surface region leads to the increase in the ionization rate and electron density here, and also accelerates the propagation speed of the jet to the dielectric surface in the atmospheric environment. Driven by the electric field force, the jet is closer to the dielectric surface, resulting in a decrease in the thickness of the cathode sheath and an increase in the surface charge density in the area to the right of the central axis. The influence of the gas flow structure leads to the shortening of the jet development distance and a decrease in the jet velocity on the upper surface. N and O also form higher fluxes on the upper surface due to the increase in the electron density. [ABSTRACT FROM AUTHOR]

The inverse Kohn–Sham (inv-KS) density-functional theory for the electron density of the Hartree–Fock (HF) wave function was revisited within the context of the optimized effective potential (HF-OEP). First, we clarify the relationship between the inv-KS and the HF-OEP within the framework of the potential-functional theory. The similarities and the differences of the approaches are then discussed on the basis of their methodological details, which motivates comparisons of the wave function provided by each method. Next, the real-space grid implementations of the inv-KS and the HF-OEP are addressed for the comparisons. The total HF energies E HF [ { φ i inv-KS } ] for the wave functions φ i inv-KS on the effective potentials optimized by the inv-KS are computed for a set of small molecules. It is found that the mean absolute deviation (MAD) of E HF [ { φ i inv-KS } ] from the HF energy is clearly smaller than the MAD of E HF [ { φ i OEP } ] , demonstrating that the inv-KS is advantageous in constructing the detailed structure of the exchange potential υx as compared with the HF-OEP. The inv-KS method is also applied to an ortho-benzyne radical known as a strongly correlated polyatomic molecule. It is revealed that the spin populations on the atomic sites computed by the UHF calculation can be faithfully reproduced by the wave functions on the inv-KS potential. [ABSTRACT FROM AUTHOR]

Electronic structures are fully determined by the exchange–correlation (XC) potential. In this work, we develop a new method to construct reliable XC potentials by properly mixing the exact exchange and the local density approximation potentials in real space. The spatially dependent mixing parameter is derived based on the derivative discontinuity of electron density and is first-principle. We derived the equations for solving the mixing parameter and proposed an approximation to simplify these equations. Based on this approximation, this new method gives reasonable predictions for the ionization energies, fundamental gaps, and singlet–triplet energy differences for various molecular systems. The impact of the approximation on the constructed XC potentials is examined, and it is found that the quality of the XC potentials can be further improved by removing the approximation. This work demonstrates that the derivative discontinuity of electron density is a promising constraint for constructing high-quality XC potentials. [ABSTRACT FROM AUTHOR]

An investigation into second-harmonic generation from magnetized anharmonic carbon nanotubes (CNTs) mounted on a silica substrate is conducted using a Gaussian laser pulse with modulated amplitude. An intense amplitude-modulated laser pulse incident on the array of CNTs displaces their electrons generating a restoration force. This restoration force is the nonlinear function of displacement of electrons, which ensures the anharmonic behavior of CNTs. Using the paraxial ray approximation, the nonlinear interaction of the incident pulse with CNTs is expressed in terms of a wave equation derived using the perturbative technique. The nonlinear current at second-harmonic frequency arises due to the perturbation of the electron density of CNTs by the ponderomotive force exerted on them by an incident pulse. Numerical outcomes validate the enhanced efficiency of the generated harmonic when considering the phenomenon of self-focusing. With the substantial optical nonlinearities of an anharmonic CNT structure, the plasmon resonance is broadened and high efficiency in generating harmonics is attained. It is seen that the augmenting of the amplitude-modulated parameter of the pulse and the external magnetic field strength enhances system nonlinearity, resulting in increased amplitude of generated second harmonics. Additionally, the effect of the heating rate of CNTs on the efficiency of the generated harmonic is also discussed. [ABSTRACT FROM AUTHOR]

Tiny NiSnO3 nanoparticles with the assistance of polyvinylpyrrolidone (PVP) are prepared to uniformly and stably "bond" on the surface of graphene to form a stable NiSnO3/RGO-PVP structure. At the same time, the excellent performance of lithium-ion batteries (LIBs) with the use of NiSnO3/RGO-PVP structure is verified through a dual combination of experiment and theory. The resulting NiSnO3/RGO-PVP structure enhanced the performance of LIBs with high cycling stability and better rate capability; even after undergoing rate performance tests at different high current densities, the NiSnO3/RGO-PVP electrode can still reach a capacity of 624 mA h g−1 at 200 mA g−1 after 400 cycles. The superior electrochemical performance of NiSnO3/RGO-PVP nanocomposites can be attributed to the synergistic effects between tiny NiSnO3 nanoparticles synthesized with the assistance of PVP and RGO, which can be verified through first-principles calculations based on DFT. The charge transfer between NiSnO3 and RGO through an electron density difference indicates a strong interaction between the two. Meanwhile, the low adsorption energies (−3.914, −0.77, and −0.65 eV), low diffusion barriers (0.025, 0.49, and 0.141 eV), and high diffusion coefficients (1.79 × 10−3, 5.38 × 10−11, and 2.97 × 10−5 cm2 s−1) of lithium ions at three different positions indicate the excellent rate performance of the NiSnO3/RGO-PVP heterostructure, which is consistent with experimental results. This work analyzes the excellent electrochemical performance of NiSnO3/RGO-PVP from the experimental results and supports the reliability of the experimental results through theoretical calculations. [ABSTRACT FROM AUTHOR]

This study provides accurate results for the electronic stopping cross sections of H, He, N, and Ne in silicon in low to intermediate energy ranges using various non-perturbative theoretical methods, including real-time time-dependent density functional theory, transport cross section, and induced-density approach. Recent experimental findings [Ntemou et al., Phys. Rev. B 107, 155145 (2023)] revealed discrepancies between the estimates of density functional theory and the observed values. We show that these discrepancies vanish by considering the nonuniform electron density of the deeper silicon bands for ion velocities approaching zero (v → 0). This indicates that mechanisms such as "elevator" and "promotion," which can dynamically excite deeper-band electrons, are active, enabling a localized free-electron gas to emulate ion energy loss, as pointed out by Lim et al. [Phys. Rev. Lett. 116, 043201 (2016)]. The observation and the description of a velocity-proportionality breakdown in electronic stopping cross sections at very low velocities are considered to be a signature of the contributions of deeper-band electrons. [ABSTRACT FROM AUTHOR]

A reduced pressure glow discharge is produced by passing a high-power pulsed DC source of 0–500 W with a frequency of 50 Hz across two parallel disk electrodes. A hydrogen peroxide aqueous solution is used as a flowing gas for discharge generation. Optical emission spectroscopy is employed to diagnose the discharge generated at a reduced pressure of 0.2 mbar with an electrode gap of 4 cm. The spectra are recorded at a power density of 9.4 mW/cm3 and typically lie in the visible wavelength range of 380–880 nm. The spectra are analyzed using the line intensity ratio method to estimate electron temperature and density. The results indicated that the electron temperature and density are, respectively, 0.87 eV and 6.4 × 1014 cm−3. [ABSTRACT FROM AUTHOR]

The titular domain-based local pair natural orbital (DLPNO) approximation is the most widely used method for extending correlated wave function models to large molecular systems, yet its fidelity for intermolecular interaction energies in large supramolecular complexes has not been thoroughly vetted. Non-covalent interactions are sensitive to tails of the electron density and involve nonlocal dispersion that is discarded or approximated if the screening of pair natural orbitals (PNOs) is too aggressive. Meanwhile, the accuracy of the DLPNO approximation is known to deteriorate as molecular size increases. Here, we test the DLPNO approximation at the level of second-order Møller–Plesset perturbation theory (MP2) and coupled-cluster theory with singles, doubles, and perturbative triples [CCSD(T)] for a variety of large supramolecular complexes. DLPNO-MP2 interaction energies are within 3% of canonical values for small dimers with ≲10 heavy atoms, but for larger systems, the DLPNO approximation is often quite poor unless the results are extrapolated to the canonical limit where the threshold for discarding PNOs is taken to zero. Counterpoise correction proves to be essential in reducing errors with respect to canonical results. For a sequence of nanoscale graphene dimers up to ( C 96 H 24 ) 2 , extrapolated DLPNO-MP2 interaction energies agree with canonical values to within 1%, independent of system size, provided that the basis set does not contain diffuse functions; these cause the DLPNO approximation to behave erratically, such that results cannot be extrapolated in a meaningful way. DLPNO-CCSD(T) calculations are typically performed using looser PNO thresholds as compared to DLPNO-MP2, but this significantly impacts accuracy for large supramolecular complexes. Standard DLPNO-CCSD(T) settings afford errors of 2–6 kcal/mol for dimers involving coronene (C24H12) and circumcoronene (C54H18), even at the DLPNO-CCSD(T1) level. [ABSTRACT FROM AUTHOR]

Helium metastable densities in the COST Reference Microplasma Jet are estimated for a variety of He/N2 admixtures and dissipated powers by applying a collisional-radiative model to absolutely calibrated optical emission spectroscopy measurements. This is accomplished by delineating the excitation mechanisms that result in the N2(C–B) and N 2 + (B–X) emission bands, the latter of which is strongly coupled to the presence of helium metastables. A number of other plasma parameters are established and discussed for each operating condition including the electron energy distribution function, reduced electric field, rate constants, and electron density. With these parameters, the reaction rates for the primary ionization pathways are also calculated, emphasizing the importance of helium metastables for discharge sustainment. Good agreement with the existing literature is found for most plasma parameters and for helium metastable densities, in particular. A clear [N2] − 1 relationship between the nitrogen concentration and density of helium metastables is demonstrated, as has been identified in previous studies in analogous atmospheric pressure plasma jets. This validates the efficacy of this optical technique for determining helium metastable densities and establishes it as a viable, and in many cases, more accessible alternative to other means of quantifying helium metastables in low-temperature plasmas. [ABSTRACT FROM AUTHOR]

We present the results of a new analysis of the literature data on electron mobility μ in dense helium gas aimed at determining the existence of a threshold density for electron self-trapping in gaseous helium as a function of temperature. We have investigated the density dependence of μ and, when available, its dependence on the electric field. The experimental data are favorably rationalized by minimizing the excess free energy of the self-localized states within the optimum fluctuation model. It is shown that the formation of electron bubbles via the self-trapping phenomenon is determined by the delicate balance between the electron thermal energy, the density dependence of the electron energy at the bottom of the conduction band in the gas, and the work necessary to expand the bubble. We show that the self-trapping phenomenon is not limited to low temperatures but occurs at any temperatures for large enough densities. [ABSTRACT FROM AUTHOR]

Quartz material irradiated by femtosecond laser has increasingly attracted widespread attention for the micro-fabrication of photonic devices. Mechanism exploration is beneficial for accelerating the digital progress of laser processing. However, the mechanism between femtosecond laser and quartz is complicated and needs further theoretical investigation. This paper established the theoretical model based on the ionization model with the Drude equation to study the space–time evolution of free electron density and its influence on the absorption coefficient, reflectivity, and ablation depth. In addition, we achieved a 10 × 10 micro-holes array with a pore size less than 10 μm, cone angle less than 2° in a 0.25 mm thick quartz on the condition of a laser pulse energy Ep = 3 μJ, scanning velocity v = 0.1 mm/s, and defocusing distance Δf = −0.3 mm via the bottom-up femtosecond laser processing. The work gives a new insight into further understanding the ablation mechanism of transparent materials etching by the femtosecond laser. It provides a practical technical scheme for preparing commercial quartz photonic devices. [ABSTRACT FROM AUTHOR]

High-accuracy molecular force field models suited for hot gases and plasmas are not as abundant as those geared toward ambient pressure and temperature conditions. Here, we present an improved version of our previous electron-density based force field model that can now account for polarization effects by adjusting the atomic valence electron contributions to match ab initio calculated Mulliken partial charges. Using a slightly modified version of the Hohenberg–Kohn theorem, we also include an improved theoretical formulation of our model when applied to systems with degenerate ground states. We present two variants of our polarizable model, fitted from ab initio reference data calculated at CCSD(T)/cc-pVTZ and CCSD(T)/CEP-31G levels of theory, that both accurately model water dimer interaction energies. Further improvements include the additional interaction components with fictitious non-spherically symmetric, yet atom-centered, electron densities and fitting the exchange and correlation coefficients against analytical expressions. The latter removes all unphysical oscillations that are observed in the previous non-polarizable variant of our force field. [ABSTRACT FROM AUTHOR]

In this study, the influence of ceramic shield characteristics, including thickness and geometry, on the transmission spectrum and electron density measurements of a ceramic shield cutoff probe (CSC) was investigated to measure high-density or process plasma. Through electromagnetic simulations and circuit modeling, we examined the measurement characteristics of the CSC based on different ceramic shield geometries. When the ceramic shield is sufficiently thin, it does not affect the CSC wave transmission characteristics. However, for a thick ceramic shield, a cutoff frequency shift of up to 3% toward the lower side can occur. This shift is attributed to the electrical properties of the ceramic material, which can function as a parasitic capacitor. In addition, when fabricating a CSC, depending on the shape of the ceramic shield or the method used to couple it with the CSC body, a cutoff frequency shift can occur toward the lower side. The simulation results were validated through experiments, revealing a cutoff frequency shift toward the lower side of up to 18.0% in the simulations and up to 11.6% in the experiments. The findings of this study could assist in high-density or processing plasma measurements using cutoff probes. [ABSTRACT FROM AUTHOR]

We experimentally investigate phase shift gained by electromagnetic radiation transmitted through a two-dimensional electron system (2DES) on a dielectric substrate. We systematically examined the dependence of the phase shift on the radiation frequency and 2DES electron density for the GaAs semiconductor substrate. A theoretical approach was developed that found good agreement with experimental results. We demonstrate a practically achievable phase shift of 105 °. Obtained findings pave the way for the design of terahertz devices that can manipulate the radiation phase in a controlled and precise manner. [ABSTRACT FROM AUTHOR]

Quantum-chemical subsystem and embedding methods require complex workflows that may involve multiple quantum-chemical program packages. Moreover, such workflows require the exchange of voluminous data that go beyond simple quantities, such as molecular structures and energies. Here, we describe our approach for addressing this interoperability challenge by exchanging electron densities and embedding potentials as grid-based data. We describe the approach that we have implemented to this end in a dedicated code, PyEmbed, currently part of a Python scripting framework. We discuss how it has facilitated the development of quantum-chemical subsystem and embedding methods and highlight several applications that have been enabled by PyEmbed, including wave-function theory (WFT) in density-functional theory (DFT) embedding schemes mixing non-relativistic and relativistic electronic structure methods, real-time time-dependent DFT-in-DFT approaches, the density-based many-body expansion, and workflows including real-space data analysis and visualization. Our approach demonstrates, in particular, the merits of exchanging (complex) grid-based data and, in general, the potential of modular software development in quantum chemistry, which hinges upon libraries that facilitate interoperability. [ABSTRACT FROM AUTHOR]

A finite element simulation model of terahertz wave propagation in plasma is developed. The equivalence of treating the plasma as a dielectric and an electrical conductor is studied in comparison. The propagation characteristics of terahertz waves in a unmagnetized plasma obtained from experimental measurements or simulations are simulated by interpolating the distribution of key parameters such as electron density and collision frequency of the external plasma. The validity of this open simulation model is verified by using the simulation data of plasma electron density generated by the independent electrochemical plasma generation model as external data. Using this model as a research tool, the propagation characteristics of terahertz waves in plasma measured by laser Thomson scattering are studied. The simulation results of the terahertz wave propagation characteristics in the plasma with and without considering the collision frequency are compared by this model. The terahertz transmission model in plasma can be used to study the propagation characteristics of terahertz waves in various inhomogeneous plasmas, which would be helpful to solve the communication "blackout" problem. [ABSTRACT FROM AUTHOR]

Despite the importance of the one-particle picture provided by the orbital paradigm, a rigorous understanding of the spatial distribution of electrons in molecules is still of paramount importance to chemistry. Considerable progress has been made following the introduction of topological approaches, capable of partitioning space into chemically meaningful regions. They usually provide atomic partitions, for example, through the attraction basins of the electron density in the quantum theory of atoms in molecules (QTAIM) or electron-pair decompositions, as in the case of the electron localization function (ELF). In both cases, the so-called electron distribution functions (EDFs) provide a rich statistical description of the electron distribution in these spatial domains. Here, we take the EDF concept to a new fine-grained limit by calculating EDFs in the QTAIM ∩ ELF intersection domains. As shown in AHn systems based on main group elements, as well as in the CO, NO, and BeO molecules, this approach provides an exquisitely detailed picture of the electron distribution in molecules, allowing for an insightful combination of the distribution of electrons between Lewis entities (such as bonds and lone pairs) and atoms at the same time. Besides mean-field calculations, we also explore the impact of electron correlation through Hartree–Fock (HF), density functional theory (DFT) (B3LYP), and CASSCF calculations. [ABSTRACT FROM AUTHOR]

This study investigates the sensitive region and safe operation voltage of single-event burnout (SEB) in lateral depletion-mode Ga2O3 MOSFET devices via technology computer aided design simulation. Based on the distribution of the electric field, carrier concentration, and electron current density when SEB occurs, the radiation damage mechanism of SEB is proposed. The mechanism of SEB in Ga2O3 MOSFET was revealed to be the result of a unique structure without a PN junction within it, which possesses gate control ability and exerts a significant influence on the conduction of the depletion region. [ABSTRACT FROM AUTHOR]

Porphyrins are prime candidates for a host of molecular electronics applications. Understanding the electronic structure and the role of anchoring groups on porphyrins is a prerequisite for researchers to comprehend their role in molecular devices at the molecular junction interface. Here, we use the density functional theory approach to investigate the influence of anchoring groups on Ni and Zn diphenylporphyrin molecules. The changes in geometry, electronic structure, and electronic descriptors were evaluated. There are minimal changes observed in geometry when changing the metal from Ni to Zn and the anchoring group. However, we find that the distribution of electron density changes when changing the anchoring group in the highest occupied and lowest unoccupied molecular orbitals. This has a direct effect on electronic descriptors such as global hardness, softness, and electrophilicity. Additionally, the optical spectra of both Ni and Zn diphenylporphyrin molecules exhibit either blue or red shifts when changing the anchoring group. These results indicate the importance of the anchoring group on the electronic structure and optical properties of porphyrin molecules. [ABSTRACT FROM AUTHOR]

Laser Thomson scattering is a minimally intrusive diagnostic technique for determining electron temperature, density, and bulk velocity in plasma systems. Advances in technology have made possible the application of Thomson scattering to electric propulsion-relevant plasma systems, with reported electron number-density detection limits as low as 1 × 10 16 m − 3 , and electron temperatures from one-to-tens eV. However, the implementation of laser Thomson scattering in large vacuum testing facilities, wherein electric propulsion devices are tested, remains a challenge. This work presents the implementation of a laser Thomson scattering system in a large vacuum test facility at the Georgia Tech High Power Electric Propulsion Laboratory. The diagnostic was optimized for maximum light-collection efficiency and ease of re-alignment while the facility is at vacuum. The high light-collection efficiency allowed reduced accumulation times to achieve the target detection limit of 1 × 10 17 m − 3 . The diagnostic is used to measure axial electron property profiles in the near-field plume of a lanthanum hexaboride hollow cathode operating at 25 A on krypton at a background pressure of 1.3 × 10 − 6 Torr—Kr. The diagnostic is quantitatively compared to similar systems in the literature. The resulting axial points, collected from 2 to 8 mm downstream of the cathode keeper orifice, are qualitatively and quantitatively compared with simulations and experimental measurements made with electrostatic probes and laser-induced fluorescence. The main quantitative difference between measured values and results is the one to two order of magnitude difference in the peak electron density, being attributed to the relative size and location of the external anode with respect to the cathode keeper. [ABSTRACT FROM AUTHOR]

The significance of solvent effects in electronic structure calculations has long been noted, and various methods have been developed to consider this effect. The reference interaction site model self-consistent field with constrained spatial electron density (RISM-SCF-cSED) is a hybrid model that combines the integral equation theory of molecular liquids with quantum chemistry. This method can consider the statistically convergent solvent distribution at a significantly lower cost than molecular dynamics simulations. Because the RISM theory explicitly considers the solvent structure, it performs well for systems where hydrogen bonds are formed between the solute and solvent molecules, which is a challenge for continuum solvent models. Taking advantage of being founded on the variational principle, theoretical developments have been made in calculating various properties and incorporating electron correlation effects. In this review, we organize the theoretical aspects of RISM-SCF-cSED and its distinctions from other hybrid methods involving integral equation theories. Furthermore, we carefully present its progress in terms of theoretical developments and recent applications. [ABSTRACT FROM AUTHOR]

In density-functional theory, the exchange–correlation (XC) energy can be defined exactly through the coupling-constant (λ) averaged XC hole n ̄ xc (r , r ′ ) , representing the probability depletion of finding an electron at r′ due to an electron at r. Accurate knowledge of n ̄ xc (r , r ′ ) has been crucial for developing XC energy density-functional approximations and understanding their performance for molecules and materials. However, there are very few systems for which accurate XC holes have been calculated since this requires evaluating the one- and two-particle reduced density matrices for a reference wave function over a range of λ while the electron density remains fixed at the physical (λ = 1) density. Although the coupled-cluster singles and doubles (CCSD) method can yield exact results for a two-electron system in the complete basis set limit, it cannot capture the electron–electron cusp using finite basis sets. Focusing on Hooke's atom as a two-electron model system for which certain analytic solutions are known, we examine the effect of this cusp error on the XC hole calculated using CCSD. The Lieb functional is calculated at a range of coupling constants to determine the λ-integrated XC hole. Our results indicate that, for Hooke's atoms, the error introduced by the description of the electron–electron cusp using Gaussian basis sets at the CCSD level is negligible compared to the basis set incompleteness error. The system-, angle-, and coupling-constant-averaged XC holes are also calculated and provide a benchmark against which the Perdew–Burke–Ernzerhof and local density approximation XC hole models are assessed. [ABSTRACT FROM AUTHOR]

Parr and Ghosh [Phys. Rev. A. 51 3564 (1995)] demonstrated that when near-exact electron densities and potentials are used, the exchange–correlation energies of first- and second-row atoms are well-described by a combination of the Fermi–Amaldi functional with a functional that is homogeneous of degree one under density scaling. Insight into this observation is provided by considering their work from the perspective of the effective homogeneity of the overall exchange–correlation functional. By considering a general form that combines the Fermi–Amaldi functional with a functional that is homogeneous of degree k, it is shown that for these atoms, the functional of Parr and Ghosh (k = 1) exhibits essentially optimal effective homogeneities on the electron-deficient side of the integer. Percentage errors in effective homogeneities are close to percentage errors in exchange–correlation energies. [ABSTRACT FROM AUTHOR]

Machine learning (ML) of kinetic energy functionals (KEFs), in particular kinetic energy density (KED) functionals, is a promising way to construct KEFs for orbital-free density functional theory (DFT). Neural networks and kernel methods including Gaussian process regression (GPR) have been used to learn Kohn–Sham (KS) KED from density-based descriptors derived from KS DFT calculations. The descriptors are typically expressed as functions of different powers and derivatives of the electron density. This can generate large and extremely unevenly distributed datasets, which complicates effective application of ML techniques. Very uneven data distributions require many training datapoints, can cause overfitting, and can ultimately lower the quality of an ML KED model. We show that one can produce more accurate ML models from fewer data by working with smoothed density-dependent variables and KED. Smoothing palliates the issue of very uneven data distributions and associated difficulties of sampling while retaining enough spatial structure necessary for working within the paradigm of KEDF. We use GPR as a function of smoothed terms of the fourth order gradient expansion and KS effective potential and obtain accurate and stable (with respect to different random choices of training points) kinetic energy models for Al, Mg, and Si simultaneously from as few as 2000 samples (about 0.3% of the total KS DFT data). In particular, accuracies on the order of 1% in a measure of the quality of energy–volume dependence B ′ = E V 0 − Δ V − 2 E V 0 + E ( V 0 + Δ V) Δ V / V 0 2 (where V0 is the equilibrium volume and ΔV is a deviation from it) are obtained simultaneously for all three materials. [ABSTRACT FROM AUTHOR]

The topology of the Ehrenfest force field (EhF) is investigated as a tool for describing local interactions in molecules and intermolecular complexes. The EhF is obtained by integrating the electronic force operator over the coordinates of all but one electron, which requires knowledge of both the electron density and the reduced pair density. For stationary states, the EhF can also be obtained as minus the divergence of the kinetic stress tensor, although this approach leads to well-documented erroneous asymptotic behavior at large distances from the nuclei. It is shown that these pathologies disappear using the electron density functions and that the EhF thus obtained displays the correct behavior in real space, with no spurious critical points or attractors. Therefore, its critical points can be unambiguously obtained and classified. Test cases, including strained molecules, isomerization reactions, and intermolecular interactions, were analyzed. Various chemically relevant facts are highlighted: for example, non-nuclear attractors are generally absent, potential hydrogen–hydrogen interactions are detected in crowded systems, and a bifurcation mechanism is observed in the isomerization of HCN. Moreover, the EhF atomic basins are less charged than those of the electron density. Although integration of the EhF over regions of real space can also be performed to yield the corresponding atomic forces, several numerical drawbacks still need to be solved if electron density functions are to be used for that purpose. Overall, the results obtained support the Ehrenfest force field as a reliable descriptor for the definition of atomic basins and molecular structure. [ABSTRACT FROM AUTHOR]

The intrinsic carrier density of 4H-SiC at temperatures ranging from 294 to 595 K was derived by analyzing a collector current in an npn-type SiC bipolar junction transistor, the structure of which was designed based on a device simulation. The obtained intrinsic carrier density was in good agreement with the value calculated from the bandgap and effective densities of states taking multiple and non-parabolic SiC bands into account. The coincidence of the intrinsic carrier density obtained by these two different approaches indicates the usefulness of the proposed method and the validity of the evaluated value of intrinsic carrier density. The temperature dependence of the bandgap was also estimated from the deduced intrinsic carrier density and compared with an empirical formula. The derived bandgap agreed well with the empirical formula showing bandgap shrinkage at high temperatures. The errors in evaluating the intrinsic carrier density and the bandgap caused by the estimation of the hole density and electron mobility in the base layer are also discussed for the proposed method. [ABSTRACT FROM AUTHOR]

Standard approximations for the exchange–correlation functional in Kohn–Sham density functional theory (KS-DFT) typically lead to unacceptably large errors when applied to strongly correlated electronic systems. Partition-DFT (PDFT) is a formally exact reformulation of KS-DFT in which the ground-state density and energy of a system are obtained through self-consistent calculations on isolated fragments, with a partition energy representing inter-fragment interactions. Here, we show how typical errors of the local density approximation (LDA) in KS-DFT can be largely suppressed through a simple approximation, the multi-fragment overlap approximation (MFOA), for the partition energy in PDFT. Our method is illustrated on simple models of one-dimensional strongly correlated linear hydrogen chains. The MFOA, when used in combination with the LDA for the fragments, improves LDA dissociation curves of hydrogen chains and produces results that are comparable to those of spin-unrestricted LDA, but without breaking the spin symmetry. MFOA also induces a correction to the LDA electron density that partially captures the correct density dimerization in strongly correlated hydrogen chains. Moreover, with an additional correction to the partition energy that is specific to the one-dimensional LDA, the approximation is shown to produce dissociation energies in quantitative agreement with calculations based on the density matrix renormalization group method. [ABSTRACT FROM AUTHOR]

Practical density functional theory (DFT) owes its success to the groundbreaking work of Kohn and Sham that introduced the exact calculation of the non-interacting kinetic energy of the electrons using an auxiliary mean-field system. However, the full power of DFT will not be unleashed until the exact relationship between the electron density and the non-interacting kinetic energy is found. Various attempts have been made to approximate this functional, similar to the exchange–correlation functional, with much less success due to the larger contribution of kinetic energy and its more non-local nature. In this work, we propose a new and efficient regularization method to train density functionals based on deep neural networks, with particular interest in the kinetic-energy functional. The method is tested on (effectively) one-dimensional systems, including the hydrogen chain, non-interacting electrons, and atoms of the first two periods, with excellent results. For atomic systems, the generalizability of the regularization method is demonstrated by training also an exchange–correlation functional, and the contrasting nature of the two functionals is discussed from a machine-learning perspective. [ABSTRACT FROM AUTHOR]

The Air-breathing Microwave Plasma CAThode (AMPCAT) has been developed for air-breathing electric propulsion in very-low Earth orbit. In this study, the standalone AMPCAT plasma characteristics are analyzed by means of several diagnostic tools and operation on xenon is compared to a conventional hollow cathode. A transition of AMPCAT extracted current from a lower (< 0.1 A) to higher-current (> --> 0.5 A) mode, triggered by increasing the negative cathode bias voltage, is accompanied by a significant rise in internal electron density and external electron temperature. The AMPCAT is coupled with a cylindrical Hall thruster in the 100–300 W power-level running on 0.5–0.7 mg/s of xenon, and the thrust is directly measured for cathode operation with both xenon and air. Stable thruster operation is demonstrated for the AMPCAT running on both propellants. For xenon, the performance is compared to a hollow cathode, which reveals matching discharge current profiles but a significantly higher thrust for the AMPCAT at low discharge voltages, approximately two times higher at 200 V. Langmuir probe measurements highlight a 30–40 V lower plasma potential in the cathode vicinity for the AMPCAT with xenon compared to both the hollow cathode and AMPCAT with air. This indicates a significantly improved coupling of cathode electrons to the thruster discharge, yielding an increased degree of ionization. Faraday probe and Wien filter results show that a larger current utilization efficiency drives the observed performance difference at low discharge voltages, rather than a significant change in ion acceleration or plume divergence. [ABSTRACT FROM AUTHOR]

Orbital-Free Density-Functional Theory (OF-DFT) is known to represent a promising alternative to the standard Kohn-Sham (KS) DFT, as it relies on the electron density alone, without the need to calculate all KS single-particle orbitals and energies. Here, we investigate the behavior of the main ingredients of this theory, which are the non-interacting kinetic-energy density (KED) and the Pauli potential, for metal slabs. We derive explicit density functionals for these quantities in the quantum limit where all electrons are in the same slab discrete level of energy, and we present numerical calculations beyond this quantum limit for slabs of various widths. We have found the first explicit KED functional for a realistic many-particle fermionic system, which we prove to be generally valid with no assumption about the KS potential. We also discuss the total non-interacting kinetic energy and the corresponding enhancement factor, which represent basic quantities for the practical implementation of OF-DFT. [ABSTRACT FROM AUTHOR]

Oxygen vacancies in indium tin oxide (ITO) thin films provide a direct route to effectively tune the free electron density and thereby, controlling the epsilon-near-zero (ENZ) cut-off wavelength, the wavelength at which the real part of permittivity crosses zero of the permittivity axis. In this report, oxygen vacancies in pulsed laser deposited ITO thin films are systematically tuned using different background gases (O 2 , N 2 , Ar, and He). ENZ cut-offs are observed for the films deposited under He and Ar gases. In contrast, no such cut-offs are observed in the case of other two gases. An ITO thin film deposited under He gas exhibits deeper resonance signal than the one deposited under Ar gas. As expected, no such dip in the resonance spectra is observed for the films deposited under O 2 and N 2 gases. This observation is directly correlated to the change in the number of oxygen vacancies under different ambient gases. A modified transfer matrix method which incorporates surface roughness as an effective medium layer is developed to describe the experimentally observed resonance spectra numerically. Angular invariancy of ENZ plasmon resonance and the difference in absorption values for ITO films deposited under different gases is understood in terms of local field intensity enhancement factor. The study presented here will certainly be very useful in understanding the ENZ plasmon resonance phenomena as a whole. Additionally, ITO films deposited under an inert gas environment could be excellent material platforms for realizing several exotic ENZ applications. [ABSTRACT FROM AUTHOR]

The Kohn-Sham theory addresses the challenge of representing the kinetic energy by re-quantizing density functional theory at a level of non-interacting electrons. It transforms the many-electron problem into a fictitious non-interacting electron problem, with the many-electron effects concealed within the exchange-correlation (XC) energy, which is expressed in terms of the electron density ρ(r). Unlike the wave function, ρ(r) can be viewed as a classical quantity, and expressing the XC energy in terms of it circumvents the need for correlated wave functions. In this work, we once again employ the re-quantization strategy and determine the XC energy using a local one-particle Schrödinger equation. The ground-state eigenfunction of the corresponding Hamiltonian is a reference point (r) dependent orbital φr,σ(u, σ′) which is subsequently used to generate the XC hole and the XC energy. The spin coordinate is denoted by σ and u is the electron-electron separation. The one-particle equation for φr,σ(u, σ′) includes a local potential vr,σ(u, σ′) that we approximate using two simple physical constraints. We assess the approximation by applying it to the helium iso-electronic series, the homogeneous electron gas, and the dissociation of the hydrogen molecule. [ABSTRACT FROM AUTHOR]

Orbital-free density functional theory (OF-DFT) holds promise to compute ground state molecular properties at minimal cost. However, it has been held back by our inability to compute the kinetic energy as a functional of electron density alone. Here, we set out to learn the kinetic energy functional from ground truth provided by the more expensive Kohn–Sham density functional theory. Such learning is confronted with two key challenges: Giving the model sufficient expressivity and spatial context while limiting the memory footprint to afford computations on a GPU and creating a sufficiently broad distribution of training data to enable iterative density optimization even when starting from a poor initial guess. In response, we introduce KineticNet, an equivariant deep neural network architecture based on point convolutions adapted to the prediction of quantities on molecular quadrature grids. Important contributions include convolution filters with sufficient spatial resolution in the vicinity of nuclear cusp, an atom-centric sparse but expressive architecture that relays information across multiple bond lengths, and a new strategy to generate varied training data by finding ground state densities in the face of perturbations by a random external potential. KineticNet achieves, for the first time, chemical accuracy of the learned functionals across input densities and geometries of tiny molecules. For two-electron systems, we additionally demonstrate OF-DFT density optimization with chemical accuracy. [ABSTRACT FROM AUTHOR]

The Fermi–Amaldi correction to the electrostatic self-repulsion of the particle density is usually regarded as a semi-classical exchange functional that happens to be exact only for one- and closed-shell two-electron systems. We show that this functional can be derived quantum-mechanically and is exact for any number of fermions or bosons of arbitrary spin as long as the particles occupy the same spatial orbital. The Fermi–Amaldi functional is also size-consistent for such systems, provided that the factor N in its expression is understood as an orbital occupation number rather than the total number of particles. These properties of the Fermi–Amaldi functional are ultimately related to the fact that it is a special case of the self-exchange energy formula. Implications of our findings are discussed. [ABSTRACT FROM AUTHOR]

In a recent study, we developed a kinetic-energy density functional that can be utilized in orbital-free quantum mechanical/molecular mechanical (OF-QM/MM) simulations. The functional includes the nonlocal term constructed from the response function of the reference system of the QM solute. The present work provides a method to combine the OF-QM/MM with a theory of solutions based on the energy representation to compute the solvation free energy of the QM solute in solution. The method is applied to the calculation of the solvation free energy Δμ of a QM water solute in an MM water solvent. It is demonstrated that Δμ is computed as −7.7 kcal/mol, in good agreement with an experimental value of −6.3 kcal/mol. We also develop a theory to map the free energy δμ due to electron density polarization onto the coordinate space of electrons. The free energy density obtained by the free-energy mapping for the QM water clarifies that each hydrogen atom makes a positive contribution (+34.7 kcal/mol) to δμ, and the oxygen atom gives the negative free energy (−71.7 kcal/mol). It is shown that the small polarization free energy −2.4 kcal/mol is generated as a result of the cancellation of these counteracting energies. These analyses are made possible by the OF-QM/MM approach combined with a statistical theory of solutions. [ABSTRACT FROM AUTHOR]

We have calculated the theoretical terahertz spectrum of the amino acid l-tyrosine using density functional theory (DFT). We tried two electron density functionals, Perdew–Burke–Ernzerhof (PBE) and PBE-d3. PBE-d3 includes dispersion corrections to build in van der Waals interactions, which play a role in intermolecular bonding. Both DFT models predicted a low-frequency mode that has not been previously reported. We designed an experiment to search for this mode. Using a deliberately thick sample, intense synchrotron radiation, low temperatures, and temperature variation has enabled us to observe a new resonance at 1.79 ±0.01 THz. While the PBE and PBE-d3 spectra are similar and both match the low-energy experimental data, overall the PBE-d3 appears to be slightly superior. Further refinement still of the functional may lead to even better agreement with experiment above 2.4 THz. [ABSTRACT FROM AUTHOR]

The first finite basis set implementation of the real-time time-dependent self-consistent field method in a dynamic (time-dependent) magnetic field using London atomic orbitals (LAOs) is presented. The accuracy of the finite basis approach using LAOs is benchmarked against numerical results from the literature for the hydrogen atom and H2 in the presence of rapidly oscillating magnetic fields. This comparison is used to inform the choice of appropriate basis sets for studies under such conditions. Remarkably, relatively modest compact LAO basis sets are sufficient to obtain accurate results. Analysis of electron dynamics in the hydrogen atom shows that LAO calculations correctly capture the time evolution of orbital occupations. The Fourier transformation of the autocorrelation function yields a power spectrum exhibiting harmonics associated with coherent emission, which closely matches the literature and further confirms the accuracy of this approach. The dynamical response of the electron density in H2 for a magnetic field parallel to the internuclear axis shows similar behavior to benchmark studies. The flexibility of this implementation is then demonstrated by considering how the dynamical response changes as a function of the orientation of the molecule relative to the applied field. At non-parallel orientations, the symmetry of the system is lowered and numerical benchmark data, which exploit cylindrical symmetry, are no-longer readily available. The present study demonstrates the utility of LAO-based calculations for extreme dynamic magnetic fields, providing a stress-test on the choice of basis. Future applications of this approach for less extreme dynamic magnetic fields are briefly discussed. [ABSTRACT FROM AUTHOR]

Atmospheric pressure plasmas generated from a helium gas with admixtures of water vapor have numerous applications in biomedicine. It is important that the chemistry of such plasmas can be tightly controlled so that they may be tailored for their intended use. In this study, computational modeling is used to vary the pulse repetition frequency of a nanosecond-pulsed, pin-to-pin He + 0.25% H 2 O discharge in the range of 1–100 kHz to determine the influence of the pulse repetition frequency on the resulting densities of reactive oxygen species and the rates of dominant reaction pathways involving them. The plasma is simulated using the 0D plasma-chemical kinetics model GlobalKin. The pulse shape is kept constant. The afterglow duration is, therefore, dependent on the repetition frequency. Analysis of the bulk plasma chemistry after the plasma has reached equilibrium shows that the peak electron density is only weakly dependent on the pulse repetition frequency. Increasing the pulse repetition frequency is shown to increase the density of H, O, and OH radicals, while the relationship between the repetition frequency and the densities of species with longer lifetimes, namely, H 2 O 2 and O 3 , is found to be more complex. These are formed throughout the afterglow, and their density depends on the availability of reactant species, the afterglow duration, and the background gas temperature. This work concludes that the pulse repetition frequency is not a simple control parameter, especially for species that are predominantly produced in the afterglow. Detailed modeling is required for accurate control of species densities using the pulse repetition frequency. [ABSTRACT FROM AUTHOR]

Density functional theory has been widely used in quantum mechanical simulations, but the search for a universal exchange-correlation (XC) functional has been elusive. Over the last two decades, machine-learning techniques have been introduced to approximate the XC functional or potential, and recent advances in deep learning have renewed interest in this approach. In this article, we review early efforts to use machine learning to approximate the XC functional, with a focus on the challenge of transferring knowledge from small molecules to larger systems. Recently, the transferability problem has been addressed through the use of quasi-local density-based descriptors, which are rooted in the holographic electron density theorem. We also discuss recent developments using deep-learning techniques that target high-level ab initio molecular energy and electron density for training. These efforts can be unified under a general framework, which will also be discussed from this perspective. Additionally, we explore the use of auxiliary machine-learning models for van der Waals interactions. [ABSTRACT FROM AUTHOR]

We present the chemical bonding and electronic properties of liquid methane at temperatures from 2000 to 4000 K and high densities of up to 3.0 g/cm3, calculated using ab initio molecular dynamics simulations in combination with the Mulliken population analysis. Bond-overlap populations and pair distribution functions are studied to investigate the evolution of electron delocalization accompanying atomic structure change as the density is increased. In addition, we also investigated the bandgap energy, electronic density of states, and spatial distribution of electron density. We observed that molecular hydrogen and C‒C bonds are formed after methane dissociates, and then the system undergoes a nonmetal–metal transition coinciding with hydrogen being transformed from the molecular to the atomic state. The C‒C bonds in the system retain covalent character, even at the highest density of 3.0 g/cm3. [ABSTRACT FROM AUTHOR]

Perovskite solar cells (PSCs) have earned considerable attention as a promising photovoltaic technology for future power generation. Spiro derivatives are often used as a hole-transporting layer (HTL) in highly efficient PSC devices. However, spiro derivatives have low hole mobility and conductivity in their native form and require complicated preparation. Therefore, using other low-cost chemical compounds that are easy to synthesize becomes essential to improve conductivity and, thus, efficiency. The compound MS-T, also known as 4,4′-(thiophene-2,5-diyl)bis(N,N-bis(4-methoxyphenyl) aniline), was intentionally theoretically designed to have a symmetrical structure. It consists of the core of a heterocyclic compound (thiadiazole), with two triphenylamine molecules attached at positions 2 and 5 to improve the electron density of the compound. The modeled PSC was numerically optimized with many significant parameters, including layer thickness, temperature, doping density, defect density, and other characteristics. This optimization was carried out using the SCAPS-1D program. Furthermore, flaws in the interfaces between the electron-transporting layer (ETL)/perovskite and HTL/perovskite were considered, and their impact on performance was also examined. The optimized PSC has an attainable efficiency of up to 30.66%. [ABSTRACT FROM AUTHOR]

The location of the H atoms in Ti, Zr, and Hf is crucial to the formation of the hydrides in these metals as it influences the crystal lattice transformation and the hydrogen diffusion involved in the hydride formation process. Although Ti, Zr, and Hf are all of hexagonal close-packed structure with similar lattice parameters, the solute H atom occupies the octahedral interstice in Ti but the tetragonal interstice in Zr and Hf, of which the origin is still mysterious. In the present work, the origin of the distinct site occupation behavior of H atom in Ti and Zr/Hf is investigated through first principles calculations. The calculated solution energies confirm that H prefers the octahedral interstice in Ti but the tetrahedral interstice in Zr and Hf. We ascribe the distinct site occupations of H in Ti and Zr/Hf to the varying Coulomb repulsion between the H (as a screened proton in the metals) and the matrix atoms against the interstitial size. The competition between the H-induced electron accumulation effect and the matrix atom debonding effect might matter as well. We propose that, as a general rule, a H atom prefers the site with a trade-off between a large space and a high electron density in metals. • Hydrogen occupies octahedral interstice in Ti but tetrahedral interstice in Zr/Hf. • H-metal atom Coulomb repulsion is responsible for the distinct site occupation of H. • H-induced electron redistribution might matter to the distinct site occupation of H. • H prefers the site with a trade-off between large space and high electron density. [ABSTRACT FROM AUTHOR]

A new nitro-nitrosyl complex [RuNO(Phen)(NO2)2OH] (1) was synthesized and characterized by X-ray diffraction, where Phen = 1,10-phenanthroline. The complex was crystallized in two different modifications without (1) and with a solvent molecule of DMF (1a). The photolysis process together with the determination of the quantum yield of NO release was investigated in acetonitrile solution using a special flow-through system for the simultaneous registration of infrared (IR) and optical absorption (UV-vis) spectra under irradiation with 450 nm light. The quantum yield of photoinduced NO release was 4.0 ± 0.2%. DFT calculations showed that the main contribution to the absorption band at 450 nm is made by the HOMO/HOMO-1 → LUMO transitions, which are represented by the transfer of electron density from the -OH and -NO2 ligands to the orbitals located on the Ru-NO bond. The dark and photoinduced cytotoxicity of the complex was studied against the human breast adenocarcinoma (MCF-7) and lung carcinoma (A549) cell lines and human non-tumor lung fibroblasts (MRC5). The complex shows a low cytotoxicity on MCF-7 cells (IC50dark = 90.6 ± 6.2 µM and IC50irr. = 95.3 ± 11.4 µM) and a moderate dark cytotoxicity on A549 and MRC5 cells (IC50dark = 33.4 ± 2.6 µM and IC50dark = 62.6 ± 3.1 µM, respectively), which slightly increases after irradiation (IC50irr. = 21.2 ± 3.3 µM and IC50irr. = 47.2 ± 2.3 µM, respectively). [ABSTRACT FROM AUTHOR]

Undifferenced and Uncombined Precise Point Positioning (UPPP) currently stands as a prominent research area, where the integration of high-precision ionospheric products holds the potential to substantially enhance accuracy and convergence performance in UPPP. Presently, the majority of external ionospheric constraints for UPPP rely on Global Ionospheric Maps (GIM). However, the accuracy and resolution of GIM fall short, imposing significant limitations on the positioning performance of UPPP. Consequently, this paper introduces the application of Computerized Ionospheric Tomography based on Machine Learning (CIT-ML) to enhance UPPP performance (PPP-CIT-ML). In this approach, we convert the three-dimensional electron density of CIT-ML into vertical total electron content (VTEC), and then it is compiled into ionospheric grid files essential for UPPP. Simultaneously, the traditional ionospheric tomography methods based on the improved algebraic reconstruction technique (IART) is also employed for UPPP (PPP-CIT-IART), alongside the ionospheric grid files broadcasted by the Center for Orbit Determination in Europe (CODE) for UPPP (PPP-CODE), where PPP-CIT-IART and PPP-CODE are used as the reference methods to test the performance of PPP-CIT-ML. In Static and Kinematic UPPP, compared to PPP-CODE, PPP-CIT-IART demonstrated average improvements in positioning accuracy and convergence performance by over 10% and 7%, respectively. PPP-CIT-ML showed average improvements in positioning accuracy and convergence performance by over 26% and 28%, respectively. The extrapolated ionospheric electron density (IED) applied to UPPP (ECIT-ML-PPP) and compared with PPP-CODE displayed average improvements in positioning accuracy by over 21% and convergence performance by over 26%. Compared with PPP-CIT-IART, ECIT-ML-PPP displayed average improvements in positioning accuracy and convergence performance by over 6% and 21%, respectively. These findings highlight that ionospheric error correction information obtained through ionospheric tomography significantly enhances the positioning accuracy and convergence performance of UPPP. Moreover, the performance enhancement achieved through machine learning-based ionospheric tomography is more pronounced. This study provides preliminary validation for the feasibility of applying machine learning-based ionospheric tomography results to navigation positioning. [ABSTRACT FROM AUTHOR]

The single-sited metallocene catalyst has attracted significant attention due to its high activity and application in olefin polymerization industry. In this work, we introduced a strategy of in situ modification of metallocene catalyst with pyrene through π–π stacking to study the effect in olefin polymerization. After activated by MMAO, the pyrene-modified metallocene catalyst exhibited high activities (up to 1333 kg mol−1 h−1) in ethylene polymerization, which was 1.9 times higher than that of the pyrene free catalyst system. This could be because the electron-donating ability of cyclopentene to the transition metal was enhanced through π–π interaction of pyrene with cyclopentene. The copolymerization of ethylene and 1-hexene was also studied. The pyrene-modified metallocene catalyst system performs with higher activity in the copolymerization with a lower monomer incorporation ratio. Density functional theory (DFT) calculations indicated the formation of π–π interaction between the Zr center with pyrene molecule leading to the increase in steric hindrance and electron density. [ABSTRACT FROM AUTHOR]

Trace iron-doped nickel–cobalt selenide with rich CoSe 2 (2 1 0)-Ni 3 Se 4 (2 0 2) heterointerfaces was successfully constructed via a simple one-step selenization reaction. The synthesized Fe-NiCoSe x /NCFF exhibits outstanding hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity with low overpotentials of 328 and 345 mV, respectively, at a high current density of 1000 mA cm−2, while maintaining stability for more than 20h. [Display omitted] Developing bifunctional electrocatalysts based on non-precious metals for overall water splitting, while maintaining high catalytic activity and stability under high current densities, remains challenging. Herein, we successfully constructred trace iron-doped nickel–cobalt selenide with abundant CoSe 2 (2 1 0)-Ni 3 Se 4 (2 0 2) heterointerfaces via a simple one-step selenization reaction. The synthesized Fe-NiCoSe x /NCFF (NCFF stands for nickel–cobalt-iron foam) exhibits outstanding hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity with low overpotentials of 328 mV for HER and 345 mV for OER at a high current density of 1000 mA cm−2, while maintaining stability for over 20 h. Additionally, the Fe-NiCoSe x /NCFF exhibits the lowest Tafel slope values for both HER (33.7 mV dec-1) and OER (55.92 mV dec-1), indicating the fastest kinetics on its surface. The Fe-NiCoSe x /NCFF features uniformly distributed micrometer-sized selenide particles with dense nanowires on their surface, providing a large reactive surface area and abundant active sites. Moreover, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses reveal that the catalyst is composed of nickel, cobalt, and iron, forming micrometer-sized particles with both crystalline and amorphous phases, thereby enhancing HER and OER performance under high current density. Density functional theory (DFT) calculations demonstrate that the heterostructure CoSe 2 (2 1 0)-Ni 3 Se 4 (2 0 2), with high electron density and suitable adsorption capacity for reaction intermediates, and low energy barriers for HER (−0.384 eV) and OER (ΔG 1st : 0.243 eV, ΔG 2nd : 0.376 eV), serves as an active center for both HER and OER. [ABSTRACT FROM AUTHOR]