Relation between T c and the defect structure of neodymium cerium cuprite Nd2−x CexCuO4−y

Neutron powder diffraction has been used to study the defect structure of neodymium cerium cuprite Nd_2−x Ce_xCuO_4±y (x=0.15). It has been shown that in addition to oxygen vacancies, O2 sites in superconducting samples may also contain a small quantity of implanted oxygen atoms positioned between copper ions and neodymium/cerium, which control the electrical charge in the Cu-O planes. The oxygen distribution among crystal lattice sites in Nd_2−x Ce_xCuO_4±y (x=0.15) as determined, the average charge of the copper ions was calculated by the method of valence sums, and a correlation was established between the charge of the copper-oxygen plane and T _c. Fiz. Tverd. Tela (St. Petersburg) 40, 177–183 (February 1998)     

Multiple ionization of argon in coincidence with projectile ions in 60–120 MeV Si q+-Ar collisions

A projectile ion-recoil ion coincidence technique has been employed to study the multiple ionization and the charge transfer processes in collisions of 60–120 MeV Si ^q+ (q = 4−14) ions with neutral argon atoms. The relative contribution of different ionization channels, namely; direct ionization, electron capture and electron loss leading to the production of slow moving multiply charged argon recoil ions have been investigated. The data reported on the present collision system result from a direct measurement in the considered impact energy for the first time. The total ionization cross-sections for the recoil ions are shown to scale as q ^1.7/E _p ^0.5 , where E _p is the energy in MeV of the projectile and q its charge state. The recoil fractions for the cases of total- and direct ionizations are found to decrease with increasing recoil charge state j. The total ionization fractions of the recoils are seen to depend on q and to show the presence of a ‘shell-effect’ of the target. Further, the fractions are found to vary as 1/j ² upto j = 8+. The average recoil charge state 〈j〉 increases slowly with q and with the number of lost or captured electrons from or into the projectile respectively. The projectile charge changing cross-sections σ _qq′ are found to decrease with increasing q for loss ionization and to increase with q for direct-and capture ionization processes respectively. The physics behind various scaling rules that are found to follow our data for different ionization processes is reviewed and discussed.     

Ionization of iridium ions in the Dresden EBIT studied by X-ray spectroscopy of direct excitation and radiative recombination processes

Ir^q+ ( 41≤q≤64) ions with open-shell configurations have been produced in the electron beam of the room-temperature Dresden Electron Beam Ion Trap (Dresden EBIT) at electron excitation energies from 2 keV to 13 keV. X-ray emission from direct excitation processes and radiative capture in krypton-like to aluminium-like iridium ions is measured with an energy dispersive Si(Li) detector. The detected X-ray lines are analyzed and compared with results from multiconfigurational Dirac-Fock (MCDF) atomic structure calculations. This allows to determine dominant produced ion charge states at different electron energies. The analysis shows that at the realized working gas pressure of 5×10^-9mbar for higher charged ions the maximum ion charge state is not preferently determined by the chosen electron beam energy needed for ionization of certain atomic substates, but by the balance between ionization and charge state reducing processes as charge exchange and radiative recombination. This behaviour is also discussed on the basis of model calculations for the resulting ion charge state distribution. Received 12 July 2001 and Received in final form 10 September 2001     

On the possibility of a forecast for off-centre configuration of Ag+ and Cu+ in alkali halide crystals

Summary The simple cut criterion based on the accurate determination of the radii of the ions in alkali halides and previously introduced by the authors for forecasting off-centre configuration of Li⁺ and F⁻ has been extended to heavy ions (Ag⁺ and Cu⁺). It has been found that this criterion is valid for the Ag⁺ ion, whereas for Cu⁺ gives a less precise forecast because of the lack in knowledge of the effective partial charge on Cu⁺ ion. It has been evidenced that the critical value of the ratior ₊ ^* /r ₊ between impurity and host ion radius which allows off-centre configuration is dependent on the impurity ion mass. Work jointly supported by the Ministero della Pubblica Istruzione and by Consiglio Nazionale delle Ricerche, Gruppo Nazionale di Struttura della Materia.     

Calculation of chemical bonds and diffusion path of Li ion in (LaLi)Ti2O6 by DV-Xα cluster method

The chemical bonds and lithium diffusion of La_4/3−y Li_3y Ti₂O₆ (y = 0.21) were investigated by using the DV-Xα cluster method. The cluster model used is the formula La₈Li₂Ti₂O₁₁. A Li ion was moved on the ab plane at z = 1/2. The Na ion was moved along the x axis in the cluster model La₈Na₂Ti₂O₁₁ for comparison. The total bond overlap population (BOP) between the moving Li ion and the other ions was calculated on the ab plane at z = 1/2. The total BOP of the Li ion along the x axis increased near the oxygen ion site, whereas the BOP of the Na ion decreased. The decrease in total BOP indicates the decrease in covalent interaction between the Na and the other ions. The change of the net charge of the Li ion was almost the same as that of the Na ion. This suggests that the smaller change of covalent interaction in the mobile Li ion determines the diffusion path of Li ion.     

AC conductivity and relaxation behavior in ion conducting polymer nanocomposite

We report the ac conductivity and relaxation behavior analysis for a heterogeneous polymer–clay nanocomposite (PNC) having composition (polyacrylonitrile)₈LiCF₃SO₃ + x wt.% dodecylamine modified montmorillonite. Charge transport behavior in an ionically conducting PNC has been analyzed systematically and correlated with the macroscopic parameters like polymer glass transition temperature and available free mobile charge carriers. Intercalation of cation coordinated polymer into the nanometric clay channels has been confirmed by high-resolution transmission electron microscopy. The electrical properties of the intercalated PNC films have been studied using complex impedance/admittance spectroscopy. Excellent correlation of relaxation behavior with polymer glass transition temperature (T _g) confirmed the objectives of the work. An analysis of dielectric relaxation indicates that PNC films are lossy when compared with polymer–salt film. This result is a direct outcome of faster ion dynamics leading to strong electrode polarization effect due to the accumulation of charge carriers at the interface.     

Specific heat and transport properties of UPt3

We have determined partial radial distribution functions describing the distribution of ions around anions and around cations in -AgI at 573 K by measuring the diffuse neutron scattering and using the method of isotopic substitution on the silver ions. The results show that it is necessary to consider all three partial diffuse structure factors (A ₊₊,A _+–, andA _––) and not just two (A ₊₊ andA _+–) as has been done previously. The pair distribution functions show that the short range order in displacements of ions from the lattice sites appears remarkably similar to the short range order in molten CuCl. Of particular note is the similarity of the Ag–Ag and the Cu–Cu correlations which show very little structure.     

Dynamical properties and electronic structure of (LaLi)TiO3 conductors

A computer simulation by a molecular dynamics method is performed to study the properties of structure and Li ion diffusion in La_4/3???x Li (LaLi)TiO₃ ;LLTO;Li ion conductors;Superionic conductors;Perovskite;Off-site;Electronic structureA computer simulation by a molecular dynamics method is performed to study the properties of structure and Li ion diffusion in La_{4/3 − x} Li Ti₂O₆ =(LaLi)TiO₃ =LLTO, which is the perovskite-type Li ion conductor. In the low Li concentration, Li ions conduct a two-dimensional motion, while Li ions diffuse a three-dimensional motion in the high Li ion concentration. The partial distribution function for Li–Ti and the diffusion paths of Li ions suggest that Li ions stay for a long time at off-site positions, which are 2.7? away from a body-centered Ti ion. The Li ion concentration dependence to the conductivity σ is in approximate agreement with experiments. The energy band dispersion and the density of states are calculated using the linear-muffin-tin-orbital method. The energy contour map shows the stable position of Li ions is off center of the vacant La sites. Both calculations suggest that the stable position of Li ions is off center of the vacant La sites. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Study of ion–solvent interactions and activation energy of LiBr in DMSO,H<Subscript>2</Subscript>O and DMSO–H<Subscript>2</Subscript>O mixtures at various temperatures

The Jones–Dole B coefficients of the electrolyte Lithium bromide (LiBr), reference salts tetra butyl ammonium tetra phenyl borate (BU₄NBPh₄), tetra butyl ammonium bromide (BU₄NBr), and potassium chloride (KCl) in dimethylsulfoxide (DMSO), water, and DMSO–water mixtures were obtained at different temperatures range from 25 to 45 °C For this, the relative viscosities were measured for Lithium bromide (LiBr) and reference salts in DMSO, water, and DMSO–water mixtures at above-mentioned temperatures. The B coefficients of these electrolytes were behaved as structure makers in DMSO, while in H₂O and DMSO–H₂O mixtures, the B-coefficient values were less positive showing the weak structure-making effect. Ionic viscosity B coefficients allow us to assess the behavior of ions in the solvent mixtures. In this study it was observed that all the values of ionic B coefficient of (Li⁺) were positive and small showing the weak structure-making effects. It was also observed that Br⁻ ions maintain negative B coefficient values in all DMSO–H₂O mixtures, except in 60% DMSO mole fraction. From this it can be concluded that Br⁻ ion behaved as a structure breaker in water and in all DMSO–H₂O mixtures except in 60% DMSO mole fraction mixtures. The low B _± values of alkali metal ions and Br⁻ ions in water are due to the breakdown of the tetrahedral structural of water and the formation of strongly structured solvated ion. It is also observed that the values of the energy of activation of the flow for LiBr are greater in DMSO–water mixtures and in pure water than in DMSO. This may be due the presence of a network of hydrogen bonds which cause the hindrance in the flow of the solution of LiBr in DMSO–water mixtures and in pure water than in DMSO.     

Near perpendicular propagation of ion cyclotron modes in a deuterium-hydrogen-oxygen fusion plasma

A dispersion relation for the near perpendicular propagation of the electromagnetic ion cyclotron wave has been derived in a fusion plasma that has deuterium as a majority species, hydrogen as a minority species and fully ionized oxygen as an impurity constituent; all being modelled by loss cone distribution functions. The wave has a frequencyω around the deuterium ion gyrofrequency-Ω_D and a wavelength much longer than its Larmor radiusγ _LD(k _⊥ γ _LD<1); the plasma itself being characterized by large ion plasma frequencies (ω _PD ² >Ω _D ² ). Two modes, a low frequency (LF) and a high frequency (HF) mode of opposite electrical energy can propagate in the plasma; the instabilities that arise are thus due to an interaction of modes of opposite energies. We find that while hydrogen tends to destabilize the plasma, the impurity oxygen ions have the reverse effect. Also the plasma is most stable when the ratios of the perpendicular components of oxygen-to-deuterium and hydrogen-to-deuterium temperatures are kept low. Detailed studies of the wave propagation characteristics and energy reveal the close resemblance of a loss cone plasma containing oxygen to a stable Maxwellian plasma in regard to wave stability, propagation and energy.     

X ray spectroscopic intercomparison between hydrogenic ions of different Z as a method for determining Lamb shifts

Novel methods for determining the 1s Lamb shift of hydrogenic ions are outlined. In one method the energy of a 2–1 transition in the hydrogenic ion of nuclear charge Z is compared to a 4–2 transition in the hydrogenic ion of charge 2Z. A second method exploits close coincidences between Lyman series transitions in ions of similar Z. This revised version was published online in August 2006 with corrections to the Cover Date.     

Concentration of Cr<Superscript>4+</Superscript> impurity ions and color centers as an indicator of saturation of forsterite crystals Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> with oxygen

The influence of the oxygen partial pressure P _{O 2} in the growth atmosphere on the coefficient of chromium distribution between the crystal and the melt of forsterite, the Cr³⁺ and Cr⁴⁺ ion contents in crystals, and the concentration of color centers induced by irradiation has been investigated. It has been established that the crystals grown at low oxygen partial pressures P _{O 2} (0.01–0.05 kPa) are characterized by low concentrations of Cr⁴⁺ ions and color centers. A change in the oxygen partial pressure to P _{O 2} ∼ 0.85 kPa leads to an increase in the Cr⁴⁺ center concentration by a factor of ∼10 and in the color center concentration by a factor of ∼5. A further increase in the oxygen partial pressure to P _{O 2} to 12 kPa remains the concentration of these centers almost unchanged. A model has been proposed according to which the intrinsic defects formed under conditions of a relative excess of oxygen leads to both the self-oxidation of chromium and the formation of color centers in the forsterite crystals under irradiation.     

Superhyperfine structure of the EPR spectra of Ce<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The EPR spectra of Ce³⁺ impurity ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals have been investigated at a frequency of ∼9.3 GHz in the temperature range 5–25 K. The effective g factors of the ground Kramers doublet of the cerium ions in three crystals are close to each other (g _‖ = 2.737, g _⊥ = 1.475 for LiYF₄:Ce³⁺). A superhyperfine structure of the EPR spectrum of Ce³⁺ ions in the LiTmF₄ Van Vleck paramagnet has been observed in the external magnetic field B oriented along the crystallographic axis c (B ‖ c). The superhyperfine structure of the EPR soectra of the Ce³⁺ ions in the LiYF₄ and LiLuF₄ diamagnetic matrices is resolved for B ⊥ c. Possible factors responsible for this pronounced difference in the properties of the systems studied have been discussed.     

Thermodynamics of the movable oxygen and conducting properties of the solid solution YBa2Cu3-xCoxO6+δ at high temperatures

High precision coulometric measurements of the equilibrium oxygen content in the solid solution YBa₂Cu_3-xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6 and 0.8, were carried out using a double-cell technique in the temperature range 600 – 850 °C and at oxygen pressure varying between 10⁻⁵ and 1 atm. The data were employed to determine the partial molar enthalpy and entropy of the movable oxygen depending on δ and x. The electrical conductivity and thermopower were also measured in the same range of the external parameters, and their dependence on the oxygen concentration was determined at different cobalt content. The data reveal several types of oxygen sites participating in the gas-solid equilibrium. The behavior of thermodynamic functions is indicative of the partial ordering of the complex species which form the structural layer Cu_1-xCo_xO_δ with variable content of oxygen and cobalt. It was shown that replacement of copper by cobalt does not result in appearance of the electronic charge carriers. The behavior of the thermopower and electric conductivity was explained with a narrow band model. The energy change with δ and x of the p-band, which dominates the conductivity, was found to follow the respective change in the oxygen partial enthalpy. Thus, electronic carriers in the layered structure of the cuprate are strongly influenced by the labile oxygen ions. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Structure and diffusion in aluminium and gallium trihalide melts from simulations based on intramolecular force laws

Diffraction studies of the liquid structure of AlCl₃, AlBr₃, GaBr₃ and GaI₃ close to their respective freezing points have revealed fourfold coordination of the trivalent metal ions, consistent with dimeric M₂X₆ molecules being the dominant species. We evaluate the species-resolved pair distribution functions and liquid structure factors in all these melts by carrying out classical molecular-dynamics simulations, based on polarizable-halogen force laws that were determined on isolated molecular monomers and dimers in the gaseous phase. We also report results for mean-square displacements and diffusion coefficients of the two species in each melt. The model reproduces the main features of the total neutron-diffraction structure factors, showing peaks due to intermediate-range order and to charge and density short-range order, and accounts for the experimental data at a good quantitative level. Direct simulation of the pair distribution functions yields agreement with the diffraction data on metal–halogen and halogen–halogen bond lengths in the melt and on the stability of the first-neighbour shell of the metal ions. We examine the temperature dependence of the liquid structure in our models for GaBr₃ and AlCl₃ and emphasize the structural role of van der Waals interactions between the halogens.     

Mössbauer spectroscopic study of iodine-intercalated Bi2Sr2CaCu2O y

Iodine-intercalated high-T _c oxide Bi₂Sr₂CaCu₂O _y was studied at 16 K using¹²⁹I Mössbauer effect. The Mössbauer spectrum shows the presence of I ₃ ^– ions which have an almost linear structure and a symmetrical charge population, and no other iodine species are found. In addition to the electronic structure of each iodine species, the analysis of the intensity ratios of the quadrupole-split transitions reveals information about the anisotropy of the recoilless fraction for each iodine atom. It cannot exclude the possibility that the I ₃ ^– ion is slightly asymmetrical and/or bent with consideration to small interactions between the I ₃ ^– ion and the neighboring Bi-O layers.     

Polymer–ion–clay interaction based model for ion conduction in intercalation-type polymer nanocomposite

A series of polymer nanocomposite films based on intercalation of (PAN)₈LiCF₃SO₃ into the nanometric clay channels of an organomodified clay has been prepared using the standard solution-casting technique. The role of organoclay concentration on polymer–ion interaction, ion–ion interaction, and ion–clay interaction in clay-based nanocomposite films has been analyzed using Fourier transform infrared (FTIR) analysis. Substantial ion dissociation is observed even at a very low clay loading (1–2 wt.%) in the nanocomposites. FTIR results suggest the presence of both uncoordinated CF₃SO₃ ⁻ (free-anions) and ion pairs in the nanocomposite evidenced by changes in CF₃SO₃ ⁻ symmetry from C3ν to Cs and marked asymmetry in the profile of degenerate δ_d(CF₃ ⁻) mode. The experimental results suggest a direct correlation of clay-assisted ion dissociation process with variation in conductivity (σ _dc) and glass transition temperature (T _g) as a function of clay concentration. A model has been proposed to explain the observed correlation on the basis of polymer–ion–clay interaction. The proposed scheme of ion transport mechanism appears to be consistent with the experimental observation.     

Cross sections for single and double ionization of atomic helium under impact by fast multiply charged ions

Expressions for the cross sections for single and double ionization of atomic helium in collisions with fast multiply charged ions are obtained in the collision parameter range υ ²≫Z≳υ, υ ₀<c, where Z and υ are, respectively, the ion charge and ion velocity, υ ₀ is the characteristic velocity of electrons in the atomic helium ground state, and c is the velocity of light. Zh. Tekh. Fiz. 68, 1–7 (March 1998)     

Fast photoprocesses in a symmetric indotricarbocyanine dye (HITC) in solutions

Spectral-kinetic and photochemical properties of HITC dye with iodide and perchlorate counterions have been studied in environments where the dye molecules exist in different ionic forms. In ethanol, the dye molecules exist as free ions; in dichlorobenzene, as contact ion pairs. Superfast transformation of non-stationary spectra in an HITC dye bleaching band is found. The observed effects are interpreted within the framework of concepts on “burning out” a notch in the contour of a non-uniformly widened vibronic band of S ₀ → S ₁-absorption. Qualitative differences in recorded absorption spectra from the dye excited electronic states for weakly and highly polar solvents are found. It is shown that the observed differences are caused by superfast charge transfer in the contact ion pairs that results in the formation of free radicals.     

Structural effects responsible for stability and solvolytic reactivity of sulfonium ions

The solvolysis rates of X‐substituted benzhydryltetrahydrothiophenium ions ( 1 ) in pure and aqueous alcohols were determined at 25 °C and compared with the rates of the corresponding benzhydryldimethylsulfonium ions ( 2 ). The linear free energy relationship equation log k = s_f(E_f + N_f) has been used to relate quantitatively the leaving group abilities of tetrahydrothiophene (THT) and dimethyl sulfide (Me₂S). It has been demonstrated that although generating a stronger base by heterolysis, substrates 1 solvolyze over lower barriers than 2 . Steric and electronic influences that determine the relative reactivities of sulfonium salts have been examined computationally at B3LYP level of theory by calculating the energy of exchange of electrofuges with different substituents between THT and dimethyl sulfide. Because of more efficiently delocalized positive charge in THT moiety, tetrahydrothiophenium ions are more stable than the corresponding dimethylsulfonium ions, regardless of an electrofuge. The Hammond–Leffler coefficient is negative (α < 0) for the rate determining heterolysis of sulfonium salts 1 and 2 . Copyright © 2011 John Wiley & Sons, Ltd.