Optical pumping of ions in buffer gases

Transient signals measured with a pulsed rf-optical pumping method are used to determine longitudinal relaxation rates for Sr⁺ ions (even isotopes) in noble gas buffers. Depolarization cross sections of the electronic spin in the Sr⁺5² S _1/2 ground state for binary collisions with rare gas atoms are deduced. The results for σ(Sr⁺5² S _1/2) in Ų are (at temperatures between 374 and 449 °K): 2·10^?5(He),4·10^?5(Ne), 5.7·10^?3(Ar), 1.8·10^?2(Kr), and 4.0·10^?2(Xe). These cross sections for the Sr⁺ ion are about two to three orders of magnitude larger than the corresponding ones for the isoelectronic neutral Rb atom. The large increase of the Sr⁺ relaxation rates is explained with the relaxation mechanism of spin-orbit coupling, taking into account two “indirect” effects of the ionic charge: the increase in the gas kinetic cross sections and the more intimate collisions of the Sr⁺ ion with the noble gas atoms. The depolarization is shown to be predominantly due to short-range interactions. A contribution to the relaxation of the Sr⁺ ion from Sr⁺-noble gas molecule formation, induced by three-body or resonant two-body collisions, could not be established for applied pressuresp between 1.5 and 15 Torr of Ar, Kr, and Xe.     

Ab initio calculations of the geometry and electronic structure of point defects in ferroelectrics with a perovskite structure

Ab initio calculations of the optimized geometry and the electronic structure of lattice defects in incipient perovskite ferroelectrics SrTiO₃ and KTaO₃ are performed in the framework of the density functional theory. The results are presented for the Li⁺ impurity ion at the A site in the KTaO₃ and SrTiO₃ ferroelectrics; the Mn²⁺, Cd²⁺, Ca²⁺, Mg²⁺, and Zn²⁺ ions at the A site and the Mn⁴⁺ and Mg²⁺ ions at the B site in the SrTiO₃ compound; and the MN _Ti ²⁺ -V _O and Mg _Ti ²⁺ -V _O complexes in the SrTiO₃ ferroelectric. The results are obtained by the cluster method with allowance made for the structural relaxation initiated by the defect and, for nonisovalent substitutional impurities, with due regard for the charge and spin states of the defect. It is established that the Ca _Sr ²⁺ , Cd _Sr ²⁺ , Mn _Ti ⁴⁺ , and Mg _Ti ²⁺ ions have a stable central position, whereas the Li _K ⁺ ion in the KTaO₃ compound and the Li _Sr ⁺ , Mn _Sr ²⁺ , and Zn _Sr ²⁺ defects in the SrTiO₃ ferroelectric are off-center ions. The shape of the multiminimum adiabatic potential and the parameters of dielectric relaxators (activation barrier, dipole moment) for polar defects are obtained. The electronic impurity levels are determined for the Li _Sr ⁺ and Mg _Ti ²⁺ neutral defects.     

New half-metallic ferromagnets: Double perovskites SR(FeM)O<Subscript>3</Subscript> (M = Sn,Ti, Zr)

In calculations using the local spin density approximation, a new group of half-metallic ferromagnets is predicted. This group comprises double perovskites Sr₂FeSnO₆, Sr₂FeTiO₆, and Sr₂ FeZrO₆—systems with one type of magnetic ions that can be obtained by diluting the magnetic sublattice of SrFeO₃ with ions of nonmagnetic pⁿ and d⁰ metals.     

Improved luminescent properties of red-emitting Ca0.54Sr0.16Eu0.08Gd0.12(MoO4)0.2(WO4)0.8 phosphor for LED application by charge compensation

The red-emitting Ca_0.54Sr_0.16Eu_0.08Gd_0.12(MoO₄)_0.2(WO₄)_0.8 phosphor is improved in the emission charateristics by charge compensation, of which chromaticity coordinates (CIE) are x=0.66 and y=0.33. Three approaches to charge compensation are investigated, namely (a) 3Ca²⁺/Sr²⁺→2Eu³⁺/Gd³⁺+vacancy, (b) 2Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+M⁺(M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ employed as a charge compensator) and (c) Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+N⁻ (N⁻ is a monovalent anion like F⁻, Cl⁻, Br⁻ and I⁻ employed as charge compensation ions). Through photoluminescent spectra analyzing the radiative and non-radiative relaxation mechanisms of luminescent system are obtained. Under 20 mA forward-bias current, one red-emitting LED is made by combining 390-405 nm-emitting LED chip and the phosphor. The red-emitting phosphor has broad prospects in LED application field.     

Variations of ionic binding energies and the distribution of charge carriers in orthorhombic La2−x Sr x CuO4

The significance of heterovalent, substitutional disorder for the distribution of charge carriers in La_2?x Sr _x CuO₄ has been investigated. Disorder is shown to cause strong variations of binding energies of the ions ranging to some eV for Sr contentsx=0.1. Balancing the energy for a hole transport, Cu³⁺+O^2?→Cu²⁺+O^?, and taking binding energy variations into account, the process is realized to become possible without consuming energy for a subset Θ for allx Cu³⁺ in one formula unit of La_2?x Sr _x CuO₄. The functions Θ(x) are presented for hole transports to apex and in-plane oxygens, respectively. The delocalization of charge carriers is interpreted to be caused by valency disorder on metal lattice sites.     

Magnetic properties of high-T c superconductors from NQR and NMR measurements

NMR and NQR spectra and spin-lattice relaxation measurements carried out in LASCO and YBCO-type crystals are presented and analyzed in order to derive insights on the correlations and spin-dynamics of the Cu²⁺ ions and on the microscopic mechanisms of high-T _c superconductivity. As an illustrative example on how the magnetic correlation length and spin dynamics properties can be extracted from the relaxation rateW, the³⁵Cl NMR data in the two-dimensional Heisenberg system Sr₂CuCl₂O₂, around the paramagnetic-antiferromagnetic (PA-AF) transition are first considered. Then the¹³⁹La NQR relaxation measurements in La_2?xSr_xCuO₄ are briefly reviewed and it is shown how a simple picture of localized Cu²⁺ magnetic moments, whose spin fluctuation times are controlled by the charge defects induced by the doping, leads in a direct way to quantitative estimates for the progressive shift, on cooling, of the spectral density of the low-frequency spin excitations towards the high frequency range. This phenomenon can be described in terms of effective spin at the Cu²⁺ ions, and its similarities with the analogous effect of progressive delocalization in Heavy Fermions systems are pointed out. Thus, the superconducting transition appears to occur in an unconventional Fermi liquid with AF correlations among itinerant pseudoparticles, possibly involving a mechanism not directly related to the magnetic correlated dynamics. In fact, a universal behavior of the relaxation rates as a function of temperature is observed, regardless of the transition temperatureT _c. The independence ofT _c from the low frequency static and dynamical spin properties is also indicated by⁸⁹Y Knight shifts and from⁶³Cu relaxation rates in systems like YBa₂Cu₄O₈ (Y124), whereT _c can be changed by atomic substitutions and by controlling the oxygen stoichiometry. The effect of an external magnetic field on the correlated spin dynamics of the AF Fermi liquid is investigated and from a comparison of Cu NQR relaxation and NMR relaxation in oriented powder of YBCO and LASCO it is shown that the external field has the small but unambiguous effect of depressing the relaxation rates aboveT _c, besides strongly enhancing them in the superconducting phase. A maximum in the ratio \({{W\left( {NQR} \right)} \mathord{\left/ {\vphantom {{W\left( {NQR} \right)} {W\left( {\vec H\left\| {\vec c} \right.} \right)}}} \right. \kern-0em} {W\left( {\vec H\left\| {\vec c} \right.} \right)}}\) is thus observed around 80 K, either in LASCO or in YBCO, again indicating that the transition could be driven by a mechanism not directly involving the spin dynamic properties. To study the role of the fluxions belowT _c ⁸⁹Y NMR shifts and spectra in oriented powders of YBCO are analyzed. Information on the spin susceptibility and on the structure of the vortex lattice is obtained. In addition, from the temperature behavior of the linewidth a motional narrowing related to flux melting is evidenced. The effective correlation time for the vortex motion is derived and it is discussed why μ⁺SR cannot detect it in view of the different rigid-lattice line broadening.     

Spin state and magnetic interaction of cobalt ions in niobium-doped cobaltites

The magnetic properties and electrical conductivity of La_1?x Sr_xCo_1?x/2Nb _x/2O₃ solid solutions with trivalent cobalt ions are studied. These solid solutions are found to be spin glasses with T _f ～ 25 K. The ferromagnetic component is most pronounced in the composition with x = 0.15. The electrical conductivity decreases with increasing strontium content. The results obtained are interpreted within a model according to which cobalt ions located in the vicinity of strontium ions reside in an intermediate-spin state and the Co³⁺-O-Co³⁺ super-exchange interaction is ferromagnetic because of the local dynamic orbital correlations.     

Time-of-flight investigation of the intensity dependence of laser-desorbed positive ions from SrF2

The intensity dependence of the total and specific yields of positive ions desorbed from SrF₂ under 193 nm and 308 nm excimer-laser irradiation has been investigated by the time-of-flight method. The following positive ion species have been detected: F⁺, Sr⁺, Sr⁺⁺, SrF⁺⁺ and SrF ₂ ⁺ . The Sr⁺ and SrF⁺ emission yields are found to increase as E ⁿ, where E represents the laser energy per pulse. The exponent n is related to defect-initiated neutral particle emission and gas-phase ionization. The influence of surface damage on this power dependence is investigated. The F⁺ emission yield showed a quite different behaviour compared to that of the Sr⁺ and SrF⁺ emission. At both wavelengths the total positive ion emission yields saturate at a certain laser energy. In the saturation regime the SrF⁺ emission vanishes and alternative emission of F⁺ and Sr⁺ was observed at both wavelengths, but the total emission yield in the saturation regime (F⁺ + Sr⁺) remained constant. A Scanning Electron Microscope (SEM) was used to investigate the damage spots after laser irradiation for thermal effects.     

Structure and magnetic properties of perovskite Sr2CuNbO6−δ

Single phase perovskite Sr₂CuNbO_6−δ with a high proportion of Cu¹⁺ ions and oxygen vacancies was synthesized by solid-state reaction. The structure was determined by Rietveld method with space group Pm3m. Isotropic g value was evaluated from electron spin resonance (ESR) measurements. The ESR result is consistent with that of magnetic susceptibility.     

Diffusion of ammonium ions in [(NH4)1−xRbx]3H(SO4)2 studied by 1H spin–lattice relaxation in the rotating frame

Translational diffusion of NH₄⁺ ions in [(NH₄)_1?xRb_x]₃H(SO₄)₂ has been evaluated quantitatively by means of ¹H spin–lattice relaxation times in the rotating frame, T_1ρ. In the high-temperature phase (phase I), the mean residence times of NH₄⁺ ions are three or four orders of magnitude larger than those of the acidic protons. In the room-temperature phase (phase II), they are two or three orders of magnitude larger than those of the acidic protons. The transition from phases II to I causes one order of magnitude enhancement in the diffusion of NH₄⁺ ions. The mean residence time of NH₄⁺ ions increases with increase in the Rb content. The similar trend is also observed in phase II.     

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⁺.     

Transferred hyperfine field of Rb2CoCl4 single crystals in the ferroelectric-incommensurate-normal phase by Rb NMR

The molecular susceptibility and paramagnetic shift of Rb₂CoCl₄ single crystals grown using the slow evaporation method were measured, and from these experimental results we obtained the transferred hyperfine interaction due to the transfer of spin density from Co²⁺ ions to Rb⁺ ions. The transferred hyperfine field was obtained for the ferroelectric, incommensurate, and normal phases. In the case of Rb(I), the transferred hyperfine interaction decreases with increasing temperature in the incommensurate phase, and increases with increasing temperature in the normal phase. The value of H_hf in the incommensurate and normal phases increases abruptly with increasing temperature in the case of Rb(II). These results indicate that the effects due to the transfer of spin density from Co²⁺ ions to the Rb(I) and Rb(II) ions are large above T_i. In particular, the effect due to the transfer of spin density to Rb(II) ions in the normal phase is very large; the variations with temperature of the transferred hyperfine interactions of the Rb(I) and Rb(II) nuclei are more or less continuous in T_c1 and T_i, and are not affected by the ferroelectric-incommensurate-normal phase transitions.     

Effect of Ca doping on the magnetic properties of Nd0.5Sr0.5MnO3 studied by electron spin resonance

The magnetic properties of Ca-doped Nd_0.5Sr_0.5MnO₃ have been studied by electron spin resonance (ESR) and dc magnetization measurements. The antiferromagnetic order and charge order are found to occur separately at T_N=200 K and T_co=150 K, respectively. Compared to the undoped Nd_0.5Sr_0.5MnO₃, the ferromagnetic correlations are suppressed by doping of the small Ca²⁺ ion. In addition, the antiferromagnetic transition temperature is enhanced to 200 K, which can be explained by an increase of superexchange interaction between Mn³⁺ and Mn⁴⁺ ions as their distance decreases.     

Ultrasonic study on the Jahn–Teller effect near different phase transitions in La1/3Sr2/3MO3 (M=Mn,Fe, Co)

The longitudinal ultrasonic velocity (V_l), magnetization and resistivity of polycrystalline La_1/3Sr_2/3MO₃ (M=Mn, Fe, Co) have been measured between 20 and 300 K. Dramatic anomalies in V_l were observed near the temperature of the charge-ordering transition (CO), charge disproportionation transition (CD), and ferromagnetic transition (FM), which are explained by the Jahn–Teller effect originating from the M ions (M=Mn, Fe, Co). However, the detailed form of these anomalies is different, which is strongly depended on the M ion's unique electronic structure. For La_1/3Sr_2/3MO₃ (M=Mn, Fe), the V_l exhibits a valley around the CO transition temperature because of the localization of the Jahn–Teller active ions (Mn³⁺, Fe⁴⁺). And due to the instability of Fe⁴⁺, the CD transition occurs in La_1/3Sr_2/3FeO₃, which results in another softening in V_l, while only normal increase is observed in La_1/3Sr_2/3MnO₃. For La_1/3Sr_2/3CoO₃, the local lattice distortion via the Jahn–Teller effect of intermediate spin Co³⁺ leads to the velocity anomaly in the ferromagnetic metallic state.     

Magnetic disorder induced enhanced magneto-resistance in La0.5Sr0.5Co1−xRuxO3

We observe a sharp increase in negative magneto-resistance ratio up to 40% for x=0.1, in La_0.5Sr_0.5Co_1−xRu_xO₃ which is due to the magnetic disorder induced by an anti-ferromagnetic interaction between Co and Ru ions. We also observe a metal to insulator and a ferromagnetic to anti-ferromagnetic transition for 0≤x≤0.3. Ruthenium (IV) ion disrupts an intermediate spin state of cobalt (Co³⁺:t_2g⁵e_g¹), forcing a double exchange mediated ferromagnetic state to an anti-ferromagnetic spin state for x≥0.2.     

Emergent phenomena in perovskite-type manganites

Perovskite-type manganites exhibit various interesting phenomena arising from complex interplay among spin, charge, orbital, and lattice degrees of freedom. One such example is the keen competition between phases with different spin/charge/orbital orders. Keen competition between antiferromagnetic metal and orbital-ordered insulator is found in the slightly electron-doped regime near Mn⁴⁺ state which is stabilized by the high oxygen-pressure condition. Another one is the emergence of ferroelectricity either induced by the magnetic ordering or independently of the magnetic ordering. As the respective examples, perovskite-type YMnO₃ and Sr_1−xBa_xMnO₃ are discussed. In the YMnO₃, the ferroelectric lattice distortion associated with the E-type spin order is observed for the first time. Displacement-type ferroelectricity with off-center magnetic ions is discovered for Sr_0.5Ba_0.5MnO₃, which shows both large polarization value and strong coupling between ferroelectricity and magnetism.     

Improvement to the exchange field acting upon Tb ions in TbIG

The spin fluctuations of the magnetic ions play an important role on the magnetic properties of the crystals and lead to a new mechanism for the Curie-Weiss susceptibility. The exchange field H_exch acting on the rare-earth ions in Tb:YIG is improved based on the temperature dependence of the spin fluctuations, which is expressed as H_exch=n₀(1+γT+βT⁻²)M_YIG. By means of the improved exchange field, the magnetic and magneto-optical properties of Tb³⁺ ions in Tb:YIG are calculated. The calculated results are in good agreement with the measured data in the temperature range from 40 to 300 K.     

Implantation of impurity ions into He II for optical spectroscopy purposes

An experimental arrangement for implantation and handling of high densities of alkaline earth ions in He II is described. First results, including mobility measurements of Sr⁺, Ba⁺, Zn⁺and Cd⁺ ions as well as optical detection of Ba⁺ ions, are reported.     

About the nature of Ni3+ magnetic centres in the LaSrAl1−xNixO4 ceramics

LaSrAl_1?x Ni _x 0₄ (x≤0.11) ceramics werer studied by EPR. It was established that Ni³⁺ ions in this compound may be in two states: a low spin one with t _2g ⁶ e _g ¹ electron configuration and high spin state with t _2g ⁵ e _g ² electron configuration. It was shown that the random distribution of La³⁺ and Sr²⁺ ions in the heavy metal sublattice leads to two kinds for each type of these centres with different degree of tetragonal distortions. The total concentration of NiO₆ isolated centres in these ceramics does not exceed 5–10 % of a total number of nickel ions at a givenx. A model, explaining these peculiarities observed in an experiment by the enhanced tendency of Ni³⁺ ions to clusterization, was proposed. It appears that even at small concentrations Ni³⁺ ions form clusters and conglomerates, whose structural characteristics of the oxygen octahedra are comparable with those in LaSrNiO₄.     

Dependence of nuclear deorientation on nuclear spin for recoils in vacuum

Time-integral measurements have been made of the vacuum deorientation of the 2⁺ and 4⁺ states in ¹⁵⁰Sm and the 6⁺ and 8⁺ states in ¹⁵⁶Gd Coulomb-excited by 133 MeV ³⁵Cl ions. The ¹⁵⁰Sm results were deduced from γ-ray angular distributions measured in coincidence with backscattered ³⁵Cl ions. In the ¹⁵⁶Gd measurements, a fixed counter array and a sandwich target were used to measure directly the differences between the γ-ray angular distributions from nuclei recoiling in vacuum and the unperturbed γ-ray angular distributions from nuclei stopped in a thick ¹⁵⁶Gd target. The measured deorientation time constants in ps are τ₂(2⁺) = 27±4; τ₂(4⁺) = 14±4; τ₂(6⁺) = 24±3; τ₂(8⁺) = 23⁺¹⁰_?6; τ₄(2⁺) = 12±2; τ₄(4⁺) = 5±3; τ₄(6⁺) = 7.6±2.5. The 8⁺ data were analyzed assuming τ₂/τ₄ = $\text{10}\text{3}$ as predicted by the Abragam-Pound theory for $\text{I ≧ 4}$ essentially independently of the degree of quadrupole admixture. The other results are consistent with this except for the 2⁺ level which shows some quadrupole effect. The present results, which show strong deorientation of high spin levels, are in contrast to earlier work on neutron deficient Er isotopes. In light of our findings we suggest that the failure to observe deorientation in the high spin states in Er is primarily due to anomalously low g-factors associated with the backbending observed in these nuclei.