Substitution effects on the bulk and surface properties of (Li,Ni)Mn<Subscript>2</Subscript>O<Subscript>4</Subscript>

Manganese oxides of spinel structure, LiMn₂O₄, Li_1-x Ni _x Mn₂O₄ (0.25 ≤ x≤ 0.75), and NiMn₂O₄, were studied by EDS, XRD, SEM, magnetic (M-H, M-T), and XPS measurements. The samples were synthesized by an ultrasound-assisted sol-gel method. EDS analysis showed good agreement with the formulations of the oxides. XRD and Rietveld refinement of X-ray data indicate that all samples crystallize in the Fd3m space group characteristic of the cubic spinel structure. The a-cell parameter ranges from a = 8.2276 Å (x = 0) to a = 8.3980 Å (x = 1). SEM results showed particle agglomerates ranging in size from 2.3 μm (x = 0) down to 0.8 μm (x = 1). Hysteresis magnetization vs. applied field curves in the 5–300K range was recorded. ZFC-FC measurements indicate the presence of two magnetic paramagnetic-ferrimagnetic transitions. The experimental Curie constant was found to vary from 5 to 7.1 cm³ K mol^?1 for the range of compositions studied (0 ≤ x ≤ 1). XPS studies of these oxides revealed the presence of Ni²⁺, Mn³⁺, and Mn⁴⁺. The experimental Ni/Mn atomic ratios obtained by XPS were in good agreement with the nominal values. A linear relationship of the average oxidation state of Mn with Ni content was observed. The oxide’s cation distributions as a function of Ni content from x = 0 ?Li⁺[Mn³⁺Mn⁴⁺]O₄ to x = 1 \( {\mathrm{Ni}}_{0.35}^{2+}{\mathrm{Mn}}_{0.65}^{3+}\left[{\mathrm{Ni}}_{0.65}^{2+}\right.\left.{\mathrm{Mn}}_{1.35}^{3+}\right]{\mathrm{O}}_4 \) were proposed.     

Neutron single-particle structure of <Superscript>48</Superscript>Ca, <Superscript>50</Superscript>Ti, <Superscript>52</Superscript>Cr, <Superscript>54</Superscript>Fe,and <Superscript>56</Superscript>Ni nuclei

The change in the neutron single-particle structure of (1f?2p)-shell magic nuclei near the Fermi energy with an increase in the number of protons in the 1f _7/2 subshell from 0 for ⁴⁸Ca to 8 for ⁵⁶Ni has been investigated. Good agreement of the experimental and estimated values of the single-particle energies E _nlj of the bound states of neutrons in these nuclei with the results of calculations within the dispersive optical model is obtained.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

Extreme-ultraviolet emissivity from Xe<Superscript>8+</Superscript> to Xe<Superscript>12+</Superscript> by using a detailed line-by-line method

A theoretical model has been developed to calculate the emissivity of low densityxenon plasmas (from Xe⁸⁺ to Xe¹²⁺) by employing a detailed lineaccounting formalism. A complete set of atomic datasuch as transition probabilities for electric (magnetic) dipoleand quadruple E1, E2, M1 and M2 and electron impact excitationcollision strength, which is accurate to fine-structure level,was calculated using a full configuration interaction formalismand was used to solve the rate equation which determines thepopulation of different levels. Detailed results are given forpure Xe¹⁰⁺ ion, which is essential for extreme-ultravioletemission at 13.5 nm, and for low density plasmas (the electron densitywas taken to be 10¹² cm^-3) at temperatures of 30, 45, 55, 65and 75 eV. The fraction of different ionization stages was obtained by acompletely coupled rate equation from neutral atom to Xe²⁰⁺ by usinga detailed configuration accounting method. The results show that theemissivity of the dipole forbidden lines of transition array4s ²4p ⁶4d ⁷5s \(\rightarrow\) 4s ²4p ⁶4d ⁸ of Xe¹⁰⁺is very sensitive to the temperature, which should be a useful tool todiagnose the temperature in EBIT plasmas.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Investigating the Double Beta Decay of <Superscript>58</Superscript>Ni

Double beta decay (β + EC, EC/EC) of ⁵⁸Ni is investigated at France’s Modane Underground Laboratory (4800 m water equivalent) using the OBELIX ultralow-background HPGe detector with a sensitive volume of 600 cm³ and a natural nickel sample of ~68% 58Ni with a mass of ~21.7 kg. After preliminary analysis of the experimental data accumulated over ~144 days, new experimental limits are obtained for the 2νβ⁺EC decay of ⁵⁸Ni to the 0⁺ ground state and the 2 ₁ ⁺ , 811 keV excited state of ⁵⁸Fe, and for the 2νEC/EC decay of ⁵⁸Ni to the 2 ₁ ⁺ , 811 keV and 2 ₂ ⁺ , 1675 keV excited states of ⁵⁸Fe. The limits are T_1/2(β⁺EC,0→0⁺) > 1.7 × 10²² yr, T_1/2(β⁺EC,0→2 ₁ ⁺ ) > 2.3 × 10²² yr, T_1/2(EC/EC,0→2 ₁ ⁺ ) > 3.3 × 10²² yr, and T_1/2(EC/EC,0→2 ₂ ⁺ ) > 3.4 × 10²² yr. Experimental limit T_1/2(0νEC/EC–res, 1918 keV > 4.1 × 10²² yr is obtained for resonant neutrinoless radiative EC/EC decay with an energy of 1918.3 keV. All limits are at 90% CL.     

Spectroscopy of the <Superscript>5</Superscript>H superheavy hydrogen isotope

The formation of the ⁵H superheavy hydrogen isotope was experimentally sought in the reactions induced by stopped π^? mesons absorbed by ⁹Be nuclei. Peaks in missing-mass spectra were observed in two reaction channels, ⁹Be(π^?, pt)X and ⁹Be(π^?, dd)X, and were attributed to the ⁵H resonance states. The lowest state has parameters Er=5.5±0.2 MeV and Г=5.4±0.5 MeV [E_r is the resonance energy measured from the (triton + two neutrons) threshold]. Therefore, ⁵H is bound more weakly than ⁴H. Excited states of ⁵H were also observed. All three resonance levels (E_1r=10.6±0.3 MeV, Г_1r=6.8±0.5 MeV; E_2r=18.5±0.4 MeV, Г_2r=4.8±1.3 MeV; E_3r=26.7±0.4 MeV, Г_3r=3.6±1.3 MeV) can decay into five free nucleons.     

Adiabatic elastic moduli in ZnSe : Mn<Superscript>2+</Superscript> and ZnSe : V<Superscript>2+</Superscript> crystals

The temperature dependences of the elastic moduli C ₄₄ (C ₁₁ ? C ₁₂)/2 and C _l = (C ₁₁ + C ₁₂ + 2C ₄₄)/2 of ZnSe : V²⁺ (impurity concentration, 6 × 10¹⁸ cm^?3) and ZnSe : Mn²⁺ (9.4 × 10²⁰ cm^?3) are measured in the temperature range 1.4–100.0 K at frequencies of 52 and 156 MHz. The temperature dependences of the adiabatic elastic moduli are derived. It is established that softening of the symmetry modules is observed only in the crystal with an impurity having orbitally degenerate states.     

Single-electron charge transfer and excitations at collisions between Bi<Superscript>4+</Superscript> ions in the kiloelectronvolt energy range

Pioneering theoretical data for single-electron charge transfer and excitations due to collisions between Bi⁴⁺ ions in the ground (6s) and metastable (6p) states are gained in the collision energy interval 5–75 keV in the center-of-mass frame. The cross sections of the processes are calculated in terms of the close-coupling method in the basis of two-electron quasi-molecular states for the Coulomb trajectory of nuclei. It is found that single-electron capture into the singlet 6s ² states of Bi³⁺ ions makes a major contribution to the charge transfer total cross section for Bi⁴⁺(6s) + Bi⁴⁺(6s) collisions (reaction 1), whereas single-electron capture into the singlet 6s6p states is the basic contributor to the total cross section in Bi⁴⁺(6s) + Bi⁴⁺(6p) collisions (reaction 2). In the collision energy interval mentioned above, the collision cross sections vary between 1.2 × 10^?17 and 1.9 × 10^?17 cm² for reaction 1 and between 3.8 × 10^?17 and 5.3 × 10^?17 cm² for reaction 2. In reaction 1, the 6s → 6p excitation cross sections vary from 0.6 × 10^?16 to 0.8 × 10^?16 cm² for the singlet channel and from 2.2 × 10^?16 to 2.8 × 10^?16 cm² for the triplet channel. The calculation results are compared with the data obtained in experiments with crossed ion beams of kiloelectronvolt energy. The fraction of metastable ions in the beams is estimated by comparing the experimental data with the weighted average theoretical results for the cross sections of reactions 1 and 2. From the data for the charge transfer cross sections, one can estimate particle losses in relativistic beams due to a change in the charge state of the ions colliding with each other in the beam because of betatron oscillations.     

Study of <Superscript>179</Superscript>Hf<Superscript><Emphasis Type="Italic">m</Emphasis>2</Superscript> excitation

Isomeric ratios of ¹⁷⁹Hf ^m2,g yields in the (γ, n) reaction and the cross section for the ¹⁷⁹Hf ^m2 population in the (α, p) reaction are measured for the first time at the end-point energies of 15.1 and 17.5 MeV for bremsstrahlung photons and 26 MeV for alpha particles. The results are σ = (1.1 ± 0.11) × 10^?27 cm² for the ¹⁷⁶Lu(α, p)¹⁷⁹Hf ^m2 reaction and Y _m2/Y _g = (6.1 ± 0.3) × 10^?6 and (3.7 ± 0.2) × 10^?6 for the ¹⁸⁰Hf(γ, n)¹⁷⁹Hf ^m22 reaction at Е _ep =15.1 and 17.5 MeV, respectively. The experimental data on the relative ¹⁷⁹Hf ^m2 yield indicate a single-humped shape of the excitation function for the ¹⁸⁰Hf(γ, n)¹⁷⁹Hf ^m2 reaction. Simulation is performed using the TALYS-1.4 and EMPIRE-3.2 codes.     

A Novel Fluorimetric Bulk Optode Membrane Based on NOS Tridentate Schiff Base for Selective Optical Sensing of Al<Superscript>3+</Superscript> Ions

A novel fluorimetric optode has been developed for the highly selective and sensitive for the determination of ultra trace amounts of Al³⁺ ions. The proposed fluorescent optode is based on the incorporation of a simple and effective fluorescent sensor tridentate NOS Schiff base N-(2-hydroxynaphthylidene)-2-aminothiophenol (H₂L) in a plasticized PVC containing KTpClPB as a lipophilic anionic additive. H₂L was synthesized by a facile one-step Schiff base reaction. The plasticized PVC-membrane displays a calibration response for Al³⁺ ions over a wide concentration range from 1.0 × 10^?9 to 4.4 × 10^?3 mol/L. The fluorescence signal of the optode membrane can be easily recovered by immersion in 0.01 M EDTA. In addition to high stability and reproducibility, the sensor shows a unique selectivity towards Al³⁺ ion with respect to common co-existing cations, particularly Ga³⁺and In³⁺. The proposed optode was applied successfully for determination of Al³⁺ in some real samples, including bottled drinking waters, bottled mineral waters and soft drinks.     

Investigation on lithium ion conductivity and structural stability of yttrium-substituted Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript>

Advanced Li-air battery architecture demands a high Li⁺ conductive solid electrolyte membrane that is electrochemically stable against metallic lithium and aqueous electrolyte. In this work, an investigation has been carried out on the microstructure, Li⁺ conduction behaviour and structural stability of Li₇La_3-x Y _x Zr₂O₁₂ (x = 0.125, 0.25 and 0.50) prepared by conventional solid-state reaction technique. The phase analysis of Li₇La_3-x Y _x Zr₂O₁₂ (x = 0.125, 0.25 and 0.50) sintered at 1200 °C by powder X-ray diffraction (PXRD) and Raman confirms the formation of high Li⁺ conductive cubic phase (\( Ia\overline{3}d \)) lithium garnets. Among the investigated lithium garnets, Li₇La_2.75Y_0.25Zr₂O₁₂ sintered at 1200 °C exhibits a maximized room temperature total (bulk + grain boundary) Li⁺ conductivity of 3.21 × 10^?4 S cm^?1 along with improved relative density of 96 %. The preliminary investigation on the structural stability of Li₇La_2.75Y_0.25Zr₂O₁₂ in the solutions of 1 M LiCl, dist. H₂O and 1 M LiOH at 30 °C/50 °C indicates that the Li₇La_2.75Y_0.25Zr₂O₁₂ is relatively stable against 1 M LiCl and dist. H₂O. Further electrochemical investigation is essential for practical application of Li₇La_2.75Y_0.25Zr₂O₁₂ as protective solid electrolyte membrane in aqueous Li-air battery.     

Intensity parameters for Er<Superscript>3+</Superscript> ions in calcium-niobium-gallium garnet crystals

Based on the analysis of the absorption spectra of Er-doped calcium-niobium-gallium garnet (Er:CNGG) crystals according to the Judd-Ofelt theory, the intensity parameters for these crystals are determined to be Θ₂ = 3.43 × 10^?20 cm² Θ₄ = 1.20 × 10^?20 cm², and Θ₆ = 0.58 × 10^?20 cm². The parameters found are compared with the intensity parameters for other laser oxide crystals. Using these intensity parameters, the probabilities of radiative transitions between the energy levels of Er³⁺ ions in CNGG crystals and the luminescence branching ratios β_JJ’ are calculated. From the measured lifetime of the ⁴ I _11/2 level of Er³⁺ ions (τ = 626 μs) and the probability of the radiative transition from this level (A = 192 s^?1), it is found that about 88% of the excitation energy in the Er:CNGG crystals is nonradiatively transferred from the ⁴ I _11/2 to the ⁴ I _13/2 level. It is suggested that an increase in the oscillator strength and in the line strength of the ⁴ I _15/2 → ² H _11/2 transition of Er³⁺ in CNGG crystals, as well as an increase in the intensity parameter Θ₂ with respect to the corresponding parameters for other garnet crystals are caused by the existence in CNGG crystals of Er³⁺ centers with the environment symmetry lower than D ₂.     

Experimental Study and Analysis of Absorption Spectra of Ni<Superscript>2+</Superscript> Ions in Nickel Orthoborate Ni<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The results of studies of the absorption spectra of nickel orthoborate Ni₃(BO₃)₂ in the range of electronic d–d-transitions are reported. The obtained data are analyzed in the framework of the crystal field theory. The Ni²⁺ ions are located in two crystallographically nonequivalent positions 2a and 4f with point symmetry groups C_2h and C₂, respectively, surrounded by six oxygen ions forming deformed octahedra. The absorption spectra exhibit three intense bands corresponding to spin-resolved transitions from the ground state of nickel ion ³A_2g (³F) to the sublevels of the ³T_2g (³F), ³T_1g (³F) and ³T_1g (³P) triplets split by the spinorbit interaction and the rhombic component of the crystal field. At temperatures below 100 K, the spectra exhibit a thin structure, in which phonon-free lines can be distinguished. Comparison of the calculated frequencies of the zero-phonon transitions with the experimental data allows estimating parameters of the crystal field acting on the nickel ions in the 2a- and 4f-positions, as well as the parameters of electrostatic interaction between the 3d electrons and spin-orbit interaction constants.     

The upconversion luminescence and magnetism in Yb<Superscript>3+</Superscript>/Ho<Superscript>3+</Superscript> co-doped LaF<Subscript>3</Subscript> nanocrystals for potential bimodal imaging

Biocompatible upconversion nanoparticles with multifunctional properties can serve as potential nanoprobes for multimodal imaging. Herein, we report an upconversion nanocrystal based on lanthanum fluoride which is developed to address the imaging modalities, upconversion luminescence imaging and magnetic resonance imaging (MRI). Lanthanide ions (Yb³⁺ and Ho³⁺) doped LaF₃ nanocrystals (LaF₃ Yb³⁺/Ho³⁺) are fabricated through a rapid microwave-assisted synthesis. The hexagonal phase LaF₃ nanocrystals exhibit nearly spherical morphology with average diameter of 9.8 nm. The inductively coupled plasma mass spectrometry (ICP-MS) analysis estimated the doping concentration of Yb³⁺ and Ho³⁺ as 3.99 and 0.41%, respectively. The nanocrystals show upconversion luminescence when irradiated with near-infrared (NIR) photons of wavelength 980 nm. The emission spectrum consists of bands centred at 542, 645 and 658 nm. The stronger green emission at 542 nm and the weak red emissions at 645 and 658 nm are assigned to ⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺, respectively. The pump power dependence of luminescence intensity confirmed the two-photon upconversion process. The nanocrystals exhibit paramagnetism due to the presence of lanthanide ion dopant Ho³⁺ and the magnetization is 19.81 emu/g at room temperature. The nanocrystals exhibit a longitudinal relaxivity (r ₁) of 0.12 s^?1 mM^?1 and transverse relaxivity (r ₂) of 28.18 s^?1 mM^?1, which makes the system suitable for developing T2 MRI contrast agents based on holmium. The LaF₃ Yb³⁺/Ho³⁺ nanocrystals are surface modified by PEGylation to improve biocompatibility and enhance further functionalisation. The PEGylated nanocrystals are found to be non-toxic up to 50 μg/mL for 48 h of incubation, which is confirmed by the MTT assay as well as morphological studies in HeLa cells. The upconversion luminescence and magnetism together with biocompatibility enables the adaptability of the present system as a nanoprobe for potential bimodal imaging.     

Lithium diffusion in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based electrodes: a joint analysis of electrochemical impedance,cyclic voltammetry,pulse chronoamperometry,and chronopotentiometry data

In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li₃V₂(PO₄)₃), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10^?9 and 3 × 10^?10 cm² s^?1, respectively, for transfer in the bulk and 10^?12 cm² s^?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10^?10 and 0.9–5 × 10^?10 cm² s^?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10^?10 cm² s^?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10^?9 cm² s^?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10^?11 cm² s^?1 for anodic and 3.4 × 10^?11 cm² s^?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li₃V₂(PO₄)₃ electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.     

Theoretical study of photoionization of the isoelectronic sequence Rb<Superscript>+</Superscript>, Sr<Superscript>2+</Superscript>, and Y<Superscript>3+</Superscript>

The photoionization cross sections for the 4p shell of ions of the Kr isoelectronic sequence Rb⁺, Sr²⁺, and Y³⁺ are calculated. The configuration interaction theory and the perturbation theory are used to describe the many-electron effects. The relativistic effects are taken into account in the Pauli-Fock approximation. The calculated resonance structure of photoionization cross sections for the 4p shell in the region below the 4s threshold associated with the autoionization of the 4s-np singly excited states and the 4p4p-nln′l′ doubly excited states reproduces the results of recent measurements of total photoabsorption cross sections for the Rb⁺, Sr²⁺, and Y³⁺ ions. It is found that, as the nuclear charge in the isoelectronic sequence increases, the ratio between the direct and correlation parts of amplitudes of the 4s-(n/?)p transition changes and, as the consequence, the minimum of the photoionization cross section of the 4s shell shifts from the continuous spectrum to the region of states of discrete spectrum. This accounts for the strong changes in the shape of the 4s-np resonances in the photoionization cross sections for the 4p shell of Rb⁺, Sr²⁺, and Y³⁺, as well as the distinction between the shapes of the 4s-6p _1/2 mirror resonance in the partial 4p _1/2 and 4p _3/2 photoionization cross sections for the Y³⁺ ion which do not suppress each other in the total photoionization cross section, as is the case for similar resonances in Rb⁺ and Sr²⁺.     

Formation of lithium-like boron and nitrogen ions in the <Superscript>4</Superscript><Emphasis Type="Italic">P</Emphasis><Subscript>5/2</Subscript> state in gaseous media

We experimentally determined the fraction of α_v of lithium-like boron B²⁺ and nitrogen N⁴⁺ ions in the ⁴ P _5/2 state having a velocity of 3.6 au that are formed upon capture of two (α₂) electrons by hydrogen-like B⁴⁺ and N⁶⁺ ions and upon capture of one (α₁) electron by helium-like (1s2s)^1,3 S metastable B³⁺ and N⁵⁺ ions in gaseous media (H₂, He, N₂, Ar), as well as upon passage through a celluloid film. In light-element media (H₂, He), α₂ increases proportional to the target thickness T _g and reaches a maximum at T _g ≈ 10¹⁶ atom/cm² (for B ions, α₂ ≈ 0.2 in H₂ and α₂ ≈ 0.4 in He). For boron and nitrogen ions passing through thin layers of heavier gases (N₂, Ne), α₂ depends considerably more weakly on T _g , and, in Ar, becomes practically constant. It is assumed that, since hydrogen and helium do not contain electrons with parallel spins, autoionizing lithium-like ions are formed as a result of successive (one by one) capture of electrons, whereas, in the heavier gases, simultaneous capture of two electrons predominates. At T _g ～ 10¹⁵ atom/cm², the fraction α₁ of boron ions is the highest in He, ～0.15, and the lowest in Ar, ～0.07, being in qualitative agreement with calculations.     

Pressure induced antiferromagnet-ferromagnet transition in La<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>CoO<Subscript>2.8</Subscript> cobaltite

The anion deficient cobaltite La_0.5Ba_0.5CoO_2.8 with theformal cobalt valence state close to 3+ has been studied as function of pressure up to6.5 GPa at different temperatures by neutron powder diffraction. At ambient pressure thecrystal structure of this compound has cubic symmetry (space group Pm3?m) and is found to become antiferromagnetic withT _N close to 250 K. Applied pressure inducesa gradual transition from the antiferromagnetic into a ferromagnetic state through a mixedmagnetic state. The transition is not accompanied by obvious changes in the macroscopiccrystal symmetry. It is suggested that the magnetic ground state strongly depends on theunit cell volume and that the transition is associated with a spin state crossover of thecobalt ions whereas the formal Co³⁺/Co⁴⁺ ratio is less importantthan expected following the double exchange scenario for the appearance offerromagnetism.     

Investigation of the structural and electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> with Cr doping

Cr-doped layered oxides Li[Li_0.2Ni_0.2???x Mn_0.6???x Cr_2x ]O₂ (x?=?0, 0.02, 0.04, 0.06) were synthesized by co-precipitation and high-temperature solid-state reaction. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TRTEM), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS). XRD patterns and HRTEM results indicate that the pristine and Cr-doped Li_1.2Ni_0.2Mn_0.6O₂ show the layered phase. The Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ shows the best electrochemical properties. The first discharge specific capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 249.6 mA h g^?1 at 0.1 C, while that of Li_1.2Ni_0.2Mn_0.6O₂ is 230.4 mA h g^?1. The capacity retaining ratio of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 97.9% compared with 93.9% for Li_1.2Ni_0.2Mn_0.6O₂ after 80 cycles at 0.2 C. The discharge capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 126.2 mA h g^?1 at 5.0 C, while that of the pristine Li_1.2Ni_0.2Mn_0.6O₂ is about 94.5 mA h g^?1. XPS results show that the content of Mn³⁺ in the Li_1.2Ni_0.2Mn_0.6O₂ can be restrained after Cr doping during the cycling, which results in restraining formation of spinel-like structure and better midpoint voltages. The lithium-ion diffusion coefficient and electronic conductivity of Li_1.2Ni_0.2Mn_0.6O₂ are enhanced after Cr doping, which is responsible for the improved rate performance of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂.