First-principles calculations of the amplitudes of the electron transition from a ligand to the 5d shell of Yb3+: KZnF3

The expressions describing the amplitudes of a transition of an electron from a ligand to vacant shells of the central ion of an impurity center are derived. The amplitudes of a transition of an electron from a ligand to the 5d shell of a rare-earth ion are calculated from first principles. The calculations are performed in the basis set of orbitals taken in the form of 5s, 5p, 4f, 5d, and 6s electron shells of the central ion and 2s and 2p electron shells of the ligands. No expansion in terms of overlap integrals is employed in the calculations. The matrix elements of the (I + S)^?1 matrix are determined in the chosen basis set of orbitals. The amplitudes thus calculated are in good agreement with those obtained by fitting of the experimental data.     

Charge density distribution and bond characterization of metal dialkyldithiocarbamate complexes (M=Co,Ni)

Electron density distribution of metal dithiocarbamate complexes, Co(S₂CNMe₂)₃ and Ni(S₂CNEt₂)₂, are studied both by single X-ray diffraction method and by theoretical quantum molecular orbital calculation. Bond characterization is made in terms of deformation density, topological analysis on total electron density and Fermi hole distribution. The cobalt(III) ion is coordinated with three ‘chemically equivalent’ planar bidentate ligands. The structure of the complex is like a ‘three-bladed propeller’. The Ni(II) ion is coordinated with two ligands in a square planar fashion. Deformation density distribution and topological analysis based on multipole model and molecular orbital calculations (DFT) are performed. The asphericity in electron density around the metal ion is clearly demonstrated; where local electron density accumulation is found at d_π directions but local electron density depletion is found at d_σ direction. The agreement between experiment and theory is good. The comparison between ligand dimer (S₂CNEt₂)₂, and metal complexes are made. With the topological analysis, the shape of valence shell charge concentration (VSCC) of each atom is illustrated. The bond characterization is made through topological properties associated with bond critical point (BCP). The linear relationship between the electron density at the bond critical point, ρ(r_c), and the bond length leads to the conclusion that ρ(r_c) is a good indicator of bond strength. The bond type is determined by the Laplacian at BCP, the total energy density at BCP and the Fermi-hole function.     

Comments about the stark effect on the energy levels of f9-electrons in cubic crystal fields

Effects of free ion wave functions and J-admixture, on the Stark split energy levels of f⁹ electron systems in cubic environments are studied. This is done by working out the example of Dy³⁺ ion in the CaF₂ matrix. It is shown that while the effect of free ion wave functions is rather small, the J-admixture has a larger effect on the Stark split levels.     

Ionic implantation of N2+ in Ni(110) at 300 K

The present work gives results of a preliminary investigation, carried out by SES, AES, LEED and ELS, on the implantation of nitrogen ions in Ni(110) as a function of ion dose and subsequent surface heat treatment at different temperatures. The fine structure in the SES spectrum is the most sensitive to implantation: peaks at 9, 17.5 and 31.5 eV are shifted towards lower energies by E = 1 eV for the first two peaks and 2.8 eV for the last. At high nitrogen doses a disordered layer is observed by LEED. The p(2 × 3) structure is obtained when the crystal is heated to 750 K. The two electron loss peaks of 4.8 and 10 eV arise from an induced electron N_2p level situated 4.8 eV below the Fermi level.     

The contribution ofK-electron capture for the production of highly charged Ne recoil ions by 156 MeV bromine impact

The recoil ion production cross sections in 2MeV/amu Br ⁿ⁺+Ne⁰→Br ^n′++Ne ^q+ were measured using a projectile ion — recoil ion coincidence technique where the final charge states of both collisions partners were detected simultaneously. Multiple ionization was found to be the dominant process for the production of low charge state recoil ions whereas the production of highly charged recoil ions is accompanied by electron capture from the Nek-shell. The derived ratio of single to double Ne-k electron capture probabilities indicates deviations from a binomial statistics distribution.     

The effects of different nano particles of Al2O3 and Ag on the MHD nano fluid flow and heat transfer in a microchannel including slip velocity and temperature jump

The forced convection of nanofluid flow in a long microchannel is studied numerically according to the finite volume approach and by using a developed computer code. Microchannel domain is under the influence of a magnetic field with uniform strength. The hot inlet nanofluid is cooled by the heat exchange with the cold microchannel walls. Different types of nanoparticles such as Al₂O₃ and Ag are examined while the base fluid is considered as water. Reynolds number are chosen as Re=10 and Re=100. Slip velocity and temperature jump boundary conditions are simulated along the microchannel walls at different values of slip coefficient for different amounts of Hartmann number. The investigation of magnetic field effect on slip velocity and temperature jump of nanofluid is presented for the first time. The results are shown as streamlines and isotherms; moreover the profiles of slip velocity and temperature jump are drawn. It is observed that more slip coefficient corresponds to less Nusselt number and more slip velocity especially at larger Hartmann number. It is recommended to use Al₂O₃-water nanofluid instead of Ag-water to increase the heat transfer rate from the microchannel walls at low values of Re. However at larger amounts of Re, the nanofluid composed of nanoparticles with higher thermal conductivity works better.     

Trapping mechanism in the afterglow process of the rare-earth activated Y2O2S phosphors

Phosphorescence properties are investigated in Y₂O₂S phosphors doped with rare-earth (lanthanoid, Ln) ions. Luminescence afterglow with a decay time of several ten milliseconds is observed at room temperature in the phosphors activated by Nd, Sm, Eu, Dy, Ho, Tm, Er, and Yb. The depths (thermal activation energies) of the traps causing the afterglow are measured with the transient luminescence method.It is concluded that the excited electron and the hole in the conduction and valence bands are trapped separately in the states (impurity levels) located in the vicinity of the Ln³⁺ ion. The trapping depths of the level range from 0.3 to 1.1 eV and are dependent on the electron affinity of the Ln³⁺ ion estimated from the energy difference between the 4fⁿ⁺¹ and the 4fⁿ configurations in the 4f shell of the ion.     

Evidence for localized excitations in MgO from electron energy-loss spectroscopy

The excited electronic states in the ionic crystal MgO have been studied by electron energy-loss spectroscopy. Structure observed above the thresholds for excitation from the Mg 2p, 2s and 1s core levels shows the final states to be predominantly excitonic levels of the Mg²⁺ ion. Comparison with the known states of the Mg²⁺ free ion indicates that solid-state shifts and splittings are small.     

Electronic structure of bivalent copper off-center complexes in SrF<Subscript>2</Subscript> crystals from data of EPR and ENDOR spectroscopy

The electronic structure of bivalent copper off-center complexes in SrF₂ crystals is calculated from experimental data obtained earlier by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. The electronic structure parameters characterizing the unpaired-electron density in the vicinity of the nucleus of a copper impurity ion are determined, and the parameters of covalent bonds between an impurity copper ion and three groups of the fluorine ions nearest to this impurity are calculated. It is demonstrated that states of the ground electron configuration of the bivalent copper impurity complex involve an admixture of excited electron configurations due to electron transfer from the ligand to 4s and 4p unfilled shells of the copper ion.     

Optical emission spectroscopic studies on laser ablated TiO2 plasma

Optical emission spectroscopic investigations of the plasma produced during Nd:YAG laser ablation of sintered TiO₂ targets, in oxygen and argon gas environments are reported. The spatial variations of electron temperature (T_e) and electron number density (N_e) are studied. The effect of oxygen/argon pressure on electron temperature (T_e) and electron number density (N_e) is presented. The kinematics of the emitted particles and expansion of plume edge are discussed. Spatio-temporal variations of various species in TiO₂ plasma were recorded and corresponding velocities were calculated. The effect of oxygen pressure on intensity of neutral/ion species and their corresponding velocities is also reported.     

High gain predictions for Ni-like Gd ion

Atomic structure data and effective collision strengths for 1s² 2s² 2p⁶ 3s² 3p⁶3d¹⁰ and 54 fine-structure levels contained in the configurations 1s² 2s² 2p⁶ 3s² 3p⁶3d⁹4l (l = s, p, d, f) for the nickel-like Gd ion. These data are used in the determination of the reduced population for the 55 fine structure levels over a wide range of electron densities (from 10²¹ to 10²³) and at various electron plasma temperatures. The gain coefficient for those transitions with positive population inversion factor are determined and plotted against the electron density.     

Subject index

We have investigated the Penning ionization of NO₂(²A₁) by He(2³S) by means of electron—ion coincidence measurements. It is possible to identify two entrance channels. The quartet state is essentially repulsive and gives rise to an electron energy spectrum similar to that found in photoionization. The doublet entrance channel is strongly attractive with a well depth D_e of 4.8 {_?0.3^+0.1 eV. Ionization out of this channel leads to very broad features in the electron energy spectrum.     

High-pressure behaviour and elastic properties of heavy rare-earth Gd monopnictides

Pressure-induced structural phase transition of gadolinium monopnictides GdX (X=As and Sb) has been studied theoretically using an inter-ionic potential theory. This method has been found quite satisfactory in case of the pnictides of rare-earth and describes the crystal properties in the framework of rigid-ion model. We have modified the ionic charge so that it may include the Coulomb-screening effect by the delocalization of f electron of the rare-earth ion. The anomalous structural properties of these compounds with many f electrons have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Gd ion with the p orbital of neighbouring pnictogen ion. Both the compounds are found to undergo from their initial NaCl (B₁) structure to body centered tetragonal (BCT) structure at high pressure and agree well with the experimental results. The BCT structure is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82–0.85. The nature of bonds between the ions is predicted by simulating the ion–ion (Gd–Gd and Gd–X) distance at high pressure. Elastic properties of these compounds have also been studied with their second-order elastic constants.     

Critical current densities and flux creep rate in Co-doped BaFe2As2 with columnar defects introduced by heavy-Ion irradiation

We report the formation of columnar defects in Co-doped BaFe₂As₂ single crystals with different heavy-ion irradiations. The formation of columnar defects by 200 MeV Au ion irradiation is confirmed by transmission electron microscopy and their density is about 40% of the irradiation dose. Magneto-optical imaging and bulk magnetization measurements reveal that the critical current density J_c is enhanced in the 200 MeV Au and 800 MeV Xe ion irradiated samples while J_c is unchanged in the 200 MeV Ni ion irradiated sample. We also find that vortex creep rates are strongly suppressed by the columnar defects. We compare the effect of heavy-ion irradiation into Co-doped BaFe₂As₂ and cuprate superconductors.     

Observation of collisionless plasma heating by strong shock waves

The heating of a plasma by collisionless shock waves is investigated by measuring the variation of magnetic field (with magnetic probes), density and electron temperature (from Thomson scattering of laser light) in the shock waves. The compression waves are produced in a tube of 14 cm diameter by the fast rising magnetic field (12 kG in 0.5Μsec) of a theta pinch. For shocks with Mach numbers between 2 and 3 propagating into a hydrogen or deuterium plasma with a localΒ of about 1 (Β=ratio of particle pressure to magnetic pressure) the measured jump in density and magnetic field across the front is 2 to 4, and the electron temperature increases in the front from 3 to 50 eV with a further rise to between 100 and 250 eV in the piston region. Only about 20% of the measured electron heating can be explained by adiabatic heating and resistive heating based on binary collisions, indicating a high turbulent plasma resistance. Both the observed electron heating and the width of the shock front, which is about 0.6 ·c/Ω _p, can be accounted for using an effective collision frequency close to the ion plasma frequencyΩ _p. The ion heating in the almost stationary shock fronts can be inferred indirectly from the steady state conservation relations. For shock waves with Mach numbersM<M _crit it seems to be consistent with an adiabatic heating process, whereas forM>M _crit the calculated ion temperatures exceed those one would except for a merely adiabatic heating.     

Fragmentation of polyatomic ions produced by electron-loss collisions of butane and isobutane molecules with ions of kiloelectronvolt energy

Fragmentation accompanying the loss of electrons by butane and isobutane (C₄H₁₀) molecules in collisions with energy H⁺, He²⁺, and Ar⁶⁺ ions of kiloelectronvolt energies is studied. The electron density functional technique is applied to C _n H_2n+2 alkane molecules and their respective C _n H _2n+2 ⁺ ions to carry out quantum-chemical calculations of the atomic spacing, electron total energy for the initial configuration of the ionizing molecules and ions in the ground state, and atomic bond breaking energy necessary to produce different ion fragments. The fragmentation energy is correlated with the fragmentation probability. It is shown that the relative cross sections of ion fragmentation depend primarily on the related energy consumption. However, the process cross section is also strongly affected by the initial configuration of C₄H₁₀ isomer molecules, as well as by the amount of dangling and arising atomic bonds involved in the formation of each ion fragment.     

Charge exchange cross sections of carbon ions

Based on experimental data on the ion charge distributions, the cross sections of single electron loss σ _{i, i + 1} and single electron capture σ _{i, i ? 1} by carbon ions with velocities (2.7–8) × 10⁸ cm/s in different gaseous media (He, N₂, and Ar) have been obtained. Regularities of the cross section variation of the electron capture and loss by carbon ions as a function of the ion velocity, ion charge, and atomic number of the target have been for the first time studied in a wide range of the initial ion charge, from i = 0 to i = 6. A qualitative agreement of the obtained results with the published data has been established for a number of other ions. Theoretical calculations of the cross sections of single electron loss by carbon ions in helium have been carried out.     

Electron energy loss spectra and X-ray photoelectron spectra of Ca2V2O7

We have measured the electron energy loss spectra of Ca₂V₂O₇ in the reflexion mode, at incident energies between 200 and 2400 eV, and the X-ray photoelectron spectra excited by Al K α radiation. The abundant loss structures observed can be correlated with the possible interband transitions, collective oscillations, and excitation of O2s and V3p electrons within the V₂O₇^4- ion. The gap width and molecular orbital (MO) spread (or splitting) is about l eV larger in the V₂O₇^4- ion than in its component VO₄^3- ion. Excitation of O2s states, which may occur together with some MO over-gap transitions, displaces the collective oscillations about 7 eV towards lower energies. Deeper V3p electrons are excited with a maximum energy loss some 7 eV above their binding energy. Cross transitions from Ca3p levels into some empty states of the V₂O₇^4- ion, or direct transitions to available states of the Ca²⁺ ion could not be unambiguously identified. The energy dependence of the excitation cross section and of the electron penetration depth results in a significant variation of the relative intensity of various losses over the investigated energy range.     

Transport and magnetic properties of disordered LixVyO2 (x=0.8 and y=0.8)

The magnetic and electron transport properties of rhombohedral Li_xV_yO₂ (x=0.8 and y=0.8) are studied. The dc susceptibility of Li_xV_yO₂ can be well fitted to the modified Curie-Weiss law, which verified the paramagnetic ground state. The magnetic hysteresis and ac susceptibility also confirm this paramagnetism. The Li_xV_yO₂ exhibits semiconducting behavior, which is explained by thermal activated process at high temperature and variable-range hopping mechanism at low temperature. Anderson localization plays an important role in both the electron transport behavior and the magnetic behavior due to the site disorder between the Li⁺ ion and V⁴⁺ ion.     

Spallative ablation of dielectrics by X-ray laser

A short laser pulse in wide range of wavelengths, from infrared to X-ray, disturbs electron–ion equilibrium and increases pressure in a heated layer. The case where the pulse duration τ _L is shorter than acoustic relaxation time t _s is considered in the paper. It is shown that this short pulse may cause thermomechanical phenomena such as spallative ablation regardless of wavelength. While the physics of electron–ion relaxation strongly depends on wavelength and various electron spectra of substances: there are spectra with an energy gap in semiconductors and dielectrics opposed to gapless continuous spectra in metals. The paper describes entire sequence of thermomechanical processes from expansion, nucleation, foaming, and nanostructuring to spallation with particular attention to spallation by X-ray pulse.