Ionization State Research Articles

Constraining the geometry of the dipping atoll 4U 1624–49 with X-ray spectroscopy and polarimetry

We present the spectro-polarimetric results obtained from simultaneous X-ray observations with IXPE, NuSTAR, and NICER of the dipping neutron star X-ray binary 4U 1624–49. This source is the most polarized Atoll source so far observed with IXPE, with a polarization degree of 2.7%±0.9% in the 2–8 keV band during the nondip phase and marginal evidence of an increasing trend with energy. The higher polarization degree compared to other Atolls can be explained by the high inclination of the system (i ≈ 60°). The spectra are well described by the combination of soft thermal emission, a Comptonized component, and reflection of soft photons off the accretion disk. During the dips, the hydrogen column density of the highly ionized absorber increases while the ionization state decreases. The Comptonized radiation seems to be the dominant contribution to the polarized signal, with additional reflected photons that contribute significantly even though their fraction in the total flux is not high.

Mean Excitation Energies of all ionization stages of all atoms with [formula omitted]

The presented work provides values of Mean Excitation Energy (MEE) for all atoms and their ions with atomic numbers 1≤Z≤86. To fill in the gaps in the available data, we propose an approximate atomic model for ions of high-Z elements, that uses a semi-empirical formula based on the Local Plasma Approximation (LPA). Despite the fact that the LPA, in its original form, poorly predicts MEE for high ionization states, a relatively simple modification utilizing a fit function can amend this shortcoming. We assess the importance of relativistic effects for the MEE for highly ionized atoms and compare the proposed formula to other approximations available for high-Z elements. We estimate the uncertainty of the presented data to be less than 40% in absolute value for the worst cases and less than 20% for most ions. This corresponds to an uncertainty of the order of few percent for the logarithm of MEE, which is the value of interest in the case of Bethe’s theory of stopping power.

Impact of dissolution medium pH and ionization state of the drug on the release performance of amorphous solid dispersions

Amorphous solid dispersions (ASDs) are widely employed as a strategy to improve oral bioavailability of poorly water soluble compounds. Typically, optimal dissolution performance from a polyvinylpyrrolidone vinyl acetate (PVPVA) based ASD is observed at relatively low drug loading limit. Above a certain drug load, termed limit of congruency (LoC), the release from ASDs significantly decreases. So far, the majority of the dissolution behavior has been tested in conditions where the drug primarily exists in unionized form. In this work, the impact of pH of the dissolution environment on the release performance of ASDs of an ionizable drug was studied. Atazanavir (ATZ), a weakly basic drug with a pKa of 4.5 was used as a model compound and PVPVA was used as a non-ionizable matrix polymer. Dissolution rate was measured using Wood's apparatus which normalizes the surface area of the dissolving tablet. The pH of the dissolution media was varied between 1 and 6.8, cover a range where ATZ exists as >99% ionized or unionized species. At pH 6.8, near complete release was observed only when the drug load was ≤ 6%. Unlike typically observed drastic decline in release behavior for PVPVA based ASDs above LoC, ATZ ASDs underwent gradual decline in dissolution behavior when the DL was increased to 8%. This was attributed to potential formation of an ATZ-PVPVA associated phase with dissolution rate slower than neat PVPVA. However, the 10% DL ASD showed negligible ATZ release. On another extreme (pH 1) where ATZ is ∼100% ionized, the dissolution rate of ATZ was faster than that of PVPVA. ASD dissolution rate was found to be slower than that of the neat drug but faster than PVPVA and interestingly, did not change with DL. This can be attributed to formation of an ionized ATZ-PVPVA phase which controls the dissolution rate of the ASD. At pH 3, where the drug is ∼97% ionized, near complete release was observed for drug loads ≤ 8%. To observe significant increase in drug loading with near complete release, >98% ionization of ATZ was required. At pH 2 where ATZ is ∼99.7% ionized, near complete release was observed for drug loads up to 30%. Furthermore, the deterioration in dissolution performance with an increase in drug load continued to be gradual at pH 2. The enhancement in dissolution performance did not correlate with solubility enhancement of ATZ due to ionization. We theorize that the enhancement in the dissolution performance due to ionization is the result of formation of an ionized ATZ-PVPVA phase which increases the hydrophilicity and the miscibility of the ASD. This can help resist water induced phase separation during ASD dissolution and therefore, result in continuous, and congruent dissolution of the drug and polymer.

Direction-dependent Effects on Global 21 cm Detection

Cosmic dawn represents a critical juncture in cosmic history when the first population of stars emerged. The astrophysical processes that govern this transformation need to be better understood. The detection of redshifted 21 cm radiation emitted from neutral hydrogen during this era offers a direct window into the thermal and ionization state of the Universe. This emission manifests as differential brightness between spin temperature and the cosmic microwave background. The SARAS experiment aims to detect the sky-averaged signal in the frequency range 40–200 MHz. SARAS’s unique design and operational strategy to float the antenna over a water body minimizes spectral features that may arise due to stratified ground beneath the antenna. However, the antenna environment can be prone to configuration changes due to variations in critical design parameters such as conductivity and antenna tilt. In this paper, we connect the variations in antenna properties to signal detection prospects. By using realistic simulations of a direction- and frequency-dependent radiation pattern of the SARAS antenna and its transfer function, we establish critical parameters and estimate bias in the detectability of different models of the global 21 cm signal. We find a correlation between the nature of chromaticity in antenna properties and the bias in the recovered spectral profiles of 21 cm signals. We also find stringent requirements for transfer function corrections, which can otherwise make detection prospects prohibitive. We finally explore a range of critical parameters that allow robust signal detection.

Chromogenic mechanisms of overglaze yellow pigment produced in Jingdezhen imperial kilns during the Ming dynasty

This study employed energy-dispersive X-ray fluorescence spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet–visible-near infrared spectrophotometry to analyse eleven overglaze pigment porcelain specimens. The results show that the colouring element of the overglaze yellow pigment of Jingdezhen imperial kilns in the Ming dynasty is Fe2O3, and most of Fe2O3 can be dissolved in the lead glaze in an ionic state to make the lead glaze yellow. The chromogenic of the overglazed yellow pigment primarily depends on the concentration and coordination field of the colouring ions. The connection between the internal structure and the appearance of the overglaze yellow pigment is discussed.

Regulating the Manganese Valence State Improves the Kinetic Properties of Manganese‐Based Cathodes

AbstractManganese (Mn)‐based lithium (Li)‐ion batteries with high energy density and low cost have recently attracted considerable attention. One drawback of Mn‐based batteries is the severe capacity attenuation caused by the Jahn‐Teller effect, which distorts the crystal structure and reduces the kinetics of Li‐ion insertion/extraction in the cathodes. In this study, the Mn valence state is regulated on the surface of Mn‐based oxide particles and oxygen vacancies are introduced to facilitate rapid Li‐ion transport and charge storage by adding succinonitrile (SN) to Mn‐based cathodes. Because of the reaction between SN and Mn‐based cathode particles, the contents of Mn3+ ions and oxygen vacancies increase, leading to an improvement in the Li‐ion kinetic properties of the cathodes as well as a reduction in the dissolution of Mn from the cathodes. By regulating the Mn valence state, Li‐ion and Li metal batteries with LiMn2O4 or Li‐rich Mn‐based layered oxide cathodes show significantly enhanced discharge capacity and improved cyclic performance. This study demonstrates that regulating the valence state of Mn ions is an effective strategy for enhancing the electrochemical performance of Mn‐based Li batteries and that adding SN to the cathodes is a cost‐effective method for mass production.

Antiferromagnetic Frustration Behavior with Face-Sharing CuAs4 Tetrahedrons in Conducting ACu6As3 (A = Li and Na).

New mixed-valence copper pnictides ACu6As3 (A = Li and Na) adopt a quasi-2D structure type, featuring alkalis and [Cu6As3]- slabs along the c-axis alternatively. The face-sharing connection between CuAs4 polyhedra leads to a higher valence state for the inside Cu ions than that of Cu ions with the other connectivity way. This is confirmed by X-ray photoemission spectroscopy results. The Cu2+ with near spin 1/2 located on bilayer triangular lattice is found to exhibit a peculiar hump in magnetic susceptibility along the c-axis and, most strikingly, nearly a constant at low temperatures from 1.8 K down to 0.4 K. Besides, high hole mobilities, 68.58 and 645.16 cm2 V-1 S-1, are observed in LiCu6As3 and NaCu6As3, respectively. These compounds provide a novel material system for researching the relationship among structure, valence state, and spin correlation in frustrated lattice.

Unveiling the Role of Solvent in Solution Phase Chemical Reactions using Deep Potential-Based Enhanced Sampling Simulations.

We have used a deep learning-based active learning strategy to develop ab initio level accurate machine-learned (ML) potential for a solution-phase reactive system. Using this ML potential, we carried out enhanced sampling simulations to sample the reaction process efficiently. Multiple transitions between the reactant and product states allowed us to calculate the converged free energy surface for the reaction. As a prototypical example, we have investigated the Menshutkin reaction, a classic bimolecular nucleophilic substitution reaction (SN2) in aqueous medium. Our analyses revealed that water stabilizes the ionic product state by enhanced solvation, facilitating the reaction and making it more spontaneous. Our approach expands the scope of studying the chemical reaction under realistic conditions, such as explicit solvents at finite temperatures, closely mimicking experiments.

Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations.

We report a theoretical DFT study of the reaction pathways for chloromethane hydrolysis over metal-exchanged zeolites (Li+, Na+, K+, and Mg2+). A cluster of 78 T atoms (T referring to Si or Al atoms), comprising the zeolite Y super cavity coupled with the sodalite cage and three hexagonal prism units (Si(78-x)Al x O129H54; x = 1 or 2), was used in the calculations. The study was carried out using the ONIOM method. The high layer was computed at M062X/6-31++G(d,p), whereas the low layer was computed at the PM6 level of theory. The energy profile was obtained by single-point calculations at the M062X/6-31++G(d,p) for the entire structure. The first step studied was the adsorption of chloromethane on the zeolite, which involves an ion-dipole interaction between the metal cation and the chlorine atom. Then, two mechanistic pathways were investigated: one via formation of an adsorbed methoxide and the other involving a direct, one-step, nucleophilic attack of the water molecule to the adsorbed chloromethane. In all systems studied, the direct mechanism showed a lower energy of activation than the route involving the methoxide intermediate. The same behavior was also observed for chloromethane methanolysis to afford dimethyl ether on the metal-exchanged zeolites. The theoretical results are in agreement with the experiments of chloromethane hydrolysis over metal-exchanged zeolite Y, explaining the formation of dimethyl ether upon chloromethane methanolysis on zeolites of low or no acidity. The transition state for the direct route resembles a SN2 process assisted by the surface, reinforcing the concept of zeolites as solid solvents, providing a polar nanoenvironment that favors and assists the formation of ionic transition states and intermediates.

Synthesis and Mechanism of a Green Scale and Corrosion Inhibitor.

A new green water treatment agent, a poly(aspartic acid)-modified polymer (PASP/5-AVA), was synthesized using polysuccinimide and 5-aminovaleric acid (5-AVA) in a hybrid system. The structure was characterized, and the scale and corrosion inhibition performance were carried out with standard static scale inhibition and electrochemical methods, respectively. The mechanism was explored using XRD, XPS, SEM, and quantum chemistry calculations. The results indicated that PASP/5-AVA exhibited better scale and corrosion inhibition performance than PASP and maintained efficacy and thermal stability of the scale inhibition effect for a long time. Mechanistic studies indicated that PASP/5-AVA interferes with the normal generation of CaCO3 and CaSO4 scales through lattice distortion and dispersion, respectively; the combined effect of an alkaline environment and terminal electron-withdrawing -COOH groups can induce the stable C- ionic state formation in -CH2- of the extended side chain, thus enhancing its chelating ability for Ca2+ ions. At the same time, the extension of the side chain length also enhances the adsorption ability of the agent on the metal surface, forming a thick film and delaying the corrosion of the metal surface. This study provides the necessary theoretical reference for the design of green scale and corrosion agents.

The Galaxy Activity, Torus, and Outflow Survey (GATOS) V. Unveiling PAH survival and resilience in the circumnuclear regions of AGNs with JWST

This study analyses JWST MIRI/MRS observations of the infrared (IR) polycyclic aromatic hydrocarbon (PAH) bands in the nuclear (sim 0.4 at 11\,mu m; sim 75\,pc) and circumnuclear regions (inner sim kpc) of local active galactic nuclei (AGNs) from the Galactic Activity, Torus, and Outflow Survey (GATOS). We examine the PAH properties in the circumnuclear regions of AGNs and the projected direction of AGN-outflows and compare them to those in star-forming regions and the innermost regions of AGNs. This study employs 4.9-28.1\,mu m sub-arcsecond angular resolution data to investigate the properties of PAHs in three nearby sources L $ sim 30-40\,Mpc). Our findings are aligned with previous JWST studies, demonstrating that the central regions of AGNs display a larger fraction of neutral PAH molecules (i.e. elevated 11.3/6.2 and 11.3/7.7\,mu m PAH ratios) in comparison to star-forming galaxies. We find that AGNs might affect not only the PAH population in the innermost region, but also in the extended regions up to sim kpc scales. By comparing our observations to PAH diagnostic diagrams, we find that, in general, regions located in the projected direction of the AGN-outflow occupy similar positions on the PAH diagnostic diagrams as those of the innermost regions of AGNs. Star-forming regions that are not affected by the AGNs in these galaxies share the same part of the diagram as star-forming galaxies. We also examined the potential of the PAH-H$_2$ diagram to disentangle AGN-versus-star-forming activity. Our results suggest that in Seyfert-like AGNs, the illumination and feedback from the AGN might affect the PAH population at nuclear and kpc scales, particularly with respect to the ionisation state of the PAH grains. However, PAH molecular sizes are rather similar. The carriers of the ionised PAH bands (6.2 and 7.7\,mu m) are less resilient than those of neutral PAH bands (11.3\,mu m), which might be particularly important for strongly AGN-host coupled systems. Therefore, caution must be applied when using PAH bands as star-formation rate indicators in these systems even at kpc scales, with the effects of the AGN being more important for ionised ones.

Synthesis and NEXAFS and XPS Characterization of Pyrochlore-Type Bi1.865Co1/2Fe1/2Ta2O9+Δ

A cubic pyrochlore with the composition Bi1.865Co1/2Fe1/2Ta2O9+Δ (space group Fd-3m, a = 10.5013(8) Å) was synthesized from oxide precursors using solid-phase reactions. These ceramics are characterized by a porous microstructure formed by randomly oriented grains of an elongated shape with a longitudinal size of 0.5–1 µm. The electronic state of cobalt and iron ions in oxide ceramics was studied by NEXAFS and XPS spectroscopy. The parameters of the XPS spectra of Bi4f, Bi5d, Ta4f, Co2p, and Fe2p ionization thresholds for a complex pyrochlore were compared with the parameters of the corresponding oxides of the transition elements. The energy position of the XPS-Ta4f and -Ta5p spectra is shifted towards lower energies compared to the binding energy in tantalum(V) oxide by 0.75 eV. According to XPS spectroscopy, bismuth and tantalum cations have the corresponding effective charge of +3 and +(5-δ). The NEXAFS-Fe2p spectrum of ceramics coincides with the spectrum of Fe2O3 in its main spectrum characteristics and indicates the content of iron ions in the oxide ceramics in the form of octahedral Fe(III) ions, and according to the character of the Co2p spectrum, cobalt ions are predominantly in the Co(II) state.

Diagnostic study on laser-produced metal hydride plasmas

The characteristics of laser-produced metal hydride plasmas have been investigated in this work. The charge state and velocity of ions were determined by employing a time-of-flight technique in conjunction with an electrostatic deflection method. The ion velocities were found to be supersonic with values in the range of 104 to 105 m/s. The proportion of hydrogen ions was found to be lower than that of titanium ions. The ion emission behavior was studied by using a Faraday cup. When the total integrated space was taken into account, the ns pulsed laser was capable of producing hydrogen ion currents greater than one hundred mA. In order to understand the plasma generation process, we performed a comparative analysis between laser-generated plasma and arc plasma, and also investigated the effect of laser power density on the composition and velocity of the ions, the ablation properties of metal hydrides, and the maintainability of hydrogen ion emission.

Effect of Ba substitution on dielectric and magnetic properties in La2MnNiO6 double perovskite

This paper reports the synthesis of single-phase La2-xBaxMnNiO6 (x = 0.0 and 0.5) double-perovskite using sol-gel auto-combustion route. ADXRD studies confirm the pure phase formation of the compound with the space group R3‾c and that no other structural transformation was observed even after Ba substitution. FESEM analysis show the formation of uniformly distributed ball-shaped nanoparticles and EDX spectra endorses the stoichiometric composition of the as prepared samples. The existence of mixed oxidation states of Ni and Mn ions is validated by XPS. The dielectric properties studied in the temperature range 100 K–320 K show the enhancement in the dielectric constant and the relaxor nature of the compound upon Ba substitution. The fitting of power law and Arrott's plot validates the presence of short-range ordering i.e. Griffith-like phase. The dielectric and magnetic properties are strongly linked and correlated based on enhanced antisite disorder (∼10 %). The ESR spectroscopy was used to calculate spin relaxation time and verify the existence of double exchange interaction in the compound.

Multiphoton Resonance Meets Tunneling Ionization: High-Efficient Photoexcitation in Strong-Field-Dressed Ions.

Tunneling ionization, a fascinating quantum phenomenon, has played the key role in the development of attosecond physics. Upon absorption of a few tens of photons, tunneling ionization creates ions in different excited states and even enables the formation of population inversion between ionic states. However, the underlying physics is still being debated. Here, we demonstrate a significant enhancement in the efficiency of multiphoton excitation when ionization of neutral molecules and resonant excitation of ions coexist in strong laser fields. It facilitates the dramatic increase in population inversion and lasing radiation in N_{2}^{+} around 1000nm pump wavelength. Utilizing the ionization-coupling theory, we discover that the synergistic interplay between tunneling ionization and multiphoton excitation enables the ionic coherence to be maximized by phase locking of the periodically created ionic dipoles and consistently maintain an optimal phase for the follow-up photoexcitation. This Letter provides new insights into the photoexcitation mechanism of ions in strong laser fields and opens up a route for optimizing ionic lasing radiations.

In Situ Detection of Interfacial Ions at the Single-Bond Level.

Detecting the ionic state at the solid-liquid interface is essential to reveal the various chemical and physical processes that occur at the interface. In this study, the adsorption states of the highly electronegative ions F- and OH- at the solid-liquid interface are detected by using the scanning tunneling microscopy break junction technique. With the active hydrogen atom of the amino group as a probe, the formed ionic hydrogen bonds are successfully detected, thereby enabling in situ monitoring of the ionic state at the solid-liquid interface. Through noise power spectral density analysis and theoretical simulations, we reveal the mechanism by which ionic hydrogen bonds at the interface affect the charge transport properties. In addition, we discover that the ionic state at the solid-liquid interface can be effectively manipulated by electric fields. Under high electric fields, the concentration of the anion near the electrode is higher, and the proportion of hydrogen bonds formed is greater than that under low electric fields. This study of the interfacial ionic state at the single-bond level provides guidance for the design of high-performance materials for energy conversion and environmental purification.

Extensive reference set and refined computational protocol for calculations of 57Fe Mössbauer parameters.

Mössbauer spectroscopy is a powerful technique for probing the local electronic structure of iron compounds, because it reports in an element-selective manner on both the oxidation state and coordination environment of the Fe ion. Computational prediction of the two main Mössbauer parameters, isomer shift (δ) and quadrupole splitting (ΔEQ), has long been targeted by quantum chemical studies, and useful protocols based on density functional theory have been proposed. Here we present an extensive curated reference set of Fe compounds that is considerably larger and more diverse than literature precedents. We make a distinction between low-temperature and high-temperature experimental subgroups. This set is employed for optimizing a refined computational protocol utilizing the scalar version of the exact 2-component (X2C) Hamiltonian with the finite nucleus approximation. Attention is devoted to having an accurate and flexible all-electron basis set for Fe. We assess the performance of several DFT methods that cover all representative families and rungs of functionals and find that hybrid functionals with ca. 25-30% exact exchange offer the best accuracy for isomer shifts. The work establishes a refined general protocol of wide applicability that achieves good performance for the prediction of isomer shifts in a wider variety of systems than before, but the limitations of DFT for quadrupole splittings are also highlighted. Finally, comparison of calculated values with high-temperature experimental results shows that the use of an empirical correction factor is required to account for the second-order Doppler shift and to achieve the same quality of correlation as with the low-temperature data.

Weak antilocalization in the topological semimetal candidate YbAuSb

We report a study of the magnetic and magnetotransport properties of YbAuSb single crystals, which were grown using the bismuth flux. The x-ray diffraction data indicate that YbAuSb crystallizes in LiGaGe-type hexagonal structure with space groupP63mc. Our magnetic measurements revealed that YbAuSb is nonmagnetic with a divalent state of ytterbium ion. The temperature-dependent electrical resistivity exhibits a metallic behavior. A cusp-like feature in transverse and longitudinal magnetoresistance is observed at the low field regime. This cusp-like feature is attributed to the weak antilocalization (WAL) effect, which is more prominent at low temperatures. The transverse magnetoconductivity in low field region follows semiclassical model∼B, which is consistent with the presence of WAL phenomena. The WAL effect in transverse and longitudinal magnetoconductance is well explained using the modified Hikami-Larkin-Nagaoka and generalized Altshuler-Aronov model, respectively. The Hall resistivity shows a linear field dependence with a positive slope, suggesting hole charge carriers dominate in electrical transport. The calculated carrier density and mobility are in the order of 1020 cm-3and 102 cm2 V-1 s-1, respectively.

Scattering of e∓ in beryllium isonuclear series: cross sections and transport characteristics

The elastic scattering of electrons and positrons by beryllium atoms and its isonuclear ion states is described in this paper in terms of differential and various angle integrated cross sections. For this element, the critical minima in the elastic differential cross sections and the optimum spin polarization sites are found. These calculations are performed using the Dirac partial wave analysis (DPWA) and a projectile-target modified complex optical model potential. Further, the Monte Carlo method is used to calculate the transport characteristics of electrons in a mixture of inert gas (He, Ar) and beryllium vapor for electric field values E/N = 1-100 Td, taking into account inelastic collisions. We studied the effect of metal vapor concentration on drift velocity, average electron energy, diffusion and mobility coefficients. Finally, we investigated the effect of beryllium vapor on the electron energy distribution function in the inert gas. On comparing present work with existing theoretical calculation, a reasonable agreement is observed.

Raman imaging unveils heme uptake in endothelial cells

Heme released from damaged and senescent red blood cells (RBCs) may contribute to oxidant-mediated cell injury. One of the recently investigated physiological processes, essential in preventing the inflammatory impact of labile heme, is its uptake from the bloodstream by endothelial cells (ECs). In this study, we investigated heme uptake by ECs starting from the model studies on the in vitro cellular level, through the endothelium layer on the ex vivo murine aortic tissues. As the cellular model, Human Aortic Endothelial Cells (HAECs) were chosen, and the concentration of labile heme was adjusted so to avoid the excessive toxic effect of the labile heme. We utilized label-free Raman imaging with two different excitation wavelengths to capture the uptake process in situ and characterize the oxidation state of the iron ion in the intercalated heme. The phenomenon of heme uptake was demonstrated in both, the healthy control C57Bl/6J and FVB animals, as well as in mice with developed atherosclerosis (ApoE/LDLR−/− mice). In the presented work, we presented for the first time Raman-based evidence on the heme uptake process by endothelial cells in both, in vitro and ex vivo systems.