Influence of the ground state of the Pr<Superscript>3+</Superscript> ion on magnetic and magnetoelectric properties of the PrFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> multiferroic

The magnetic, magnetoelectric, and magnetoelastic properties of a PrFe₃(BO₃)₄ single crystal and the phase transitions induced in this crystal by the magnetic field are studied both experimentally and theoretically. Unlike the previously investigated ferroborates, this material is characterized by a singlet ground state of the rare-earth ion. It is found that, below T _N = 32 K, the magnetic structure of the crystal in the absence of the magnetic field is uniaxial (l ∥ c), while, in a strong magnetic field H ∥ c (H _cr ～ 43 kOe at T = 4.2 K), a Fe³⁺ spin reorientation to the basal plane takes place. The reorientation is accompanied by anomalies in magnetization, magnetostriction, and electric polarization. The threshold field values determined in the temperature interval 2–32 K are used to plot an H-T phase diagram. The contribution of the Pr³⁺ ion ground state to the parameters under study is revealed, and the influence of the praseodymium ion on the magnetic and magnetoelectric properties of praseodymium ferroborate is analyzed.     

High-pressure effects on the crystal and magnetic structure of managanites

Nuetron diffraction studies of high-pressure effects on the crystal and magnetic structure of A_1-x A _x ^′ MnO₃ manganites (A = Pr, La; A′ = Sr, Ca, Na) are reviewed. High pressure leads to various changes in the magnetic structure of manganites: the appearance of a new A-type antiferromagnetic (AFM) state in compounds with the initial ferromagnetic (FM) or pseudo-CE type AFM state, such as La_{1 ? x} Ca _x MnO₃ (x = 0.25, 0.33), Pr_{1 ? x} Sr _x MnO₃ (x = 0.48), Pr_0.7Ca_0.3Mn_{1 ? y} Fe _y O₃ (y = 0, 0.1), Pr_{1 ? x} Na _x MnO₃ (x = 0.2, 0.25); and the appearance of a new C-type AFM state in the Pr_0.44Sr_0.56MnO₃ compound with the initial A-type AFM state. The observed changes in the magnetic structure and the behavior of the transition temperature to the FM state under high pressure are discussed in the framework of the current theoretical concepts.     

Role of structure imperfection in the formation of the magnetotransport properties of rare-earth manganites with a perovskite structure

The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La_0.3Ln_0.3Sr_0.3Mn_1.1O_3–δ manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, ⁵⁵Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3?c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, or Eu³⁺ when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure, which contains anion and cation vacancies. The decrease in the temperatures of the metal–semiconductor (T _ms) and ferromagnet–paramagnet (T _C) phase transitions and the increase in electrical resistivity ρ and activation energy E _a with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3d ⁴(Mn³⁺)–2p ⁶(O^2–)–3d ³(Mn⁴⁺)–V ^(a)–3d ⁴(Mn³⁺). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric ⁵⁵Mn NMR spectra support the high-frequency electronic double exchange Mn³⁺(3d ⁴) ? O^2–(2p ⁶) ? Mn⁴⁺(3d ³) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition–structure imperfection–property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the magnetic, magnetotransport, and magnetoresistance properties of rare-earth perovskite manganites.     

Electronic and Magnetic States of Pr and Mn in the Pr<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> Films Studied by XANES and XMCD Spectroscopy

The spectral dependences of X-ray absorption near-edge spectroscopy (XANES) and X-ray magnetic circular dichroism (XMCD) and the field dependences of XMCD near the K edge of Mn and the L_2,3 edges of Pr in the Pr_0.8Sr_0.2MnO₃ and Pr_0.6Sr_0.4MnO₃ films at T = 90 K are studied. The spectral dependences point to a mixed valence state of Mn and Pr in the films. It is found that, as compared to XANES, XMCD is more sensitive to the valence state of Pr⁴⁺. The field dependences of XMCD point to ferromagnetic behavior of Mn ions and the Van Vleck paramagnetism of Pr ions, which makes a significant contribution to the total magnetization of the films. It is shown that as the Sr concentration increases, the XMCD intensity at the K edge of Mn increases, which indicates a growth of the total magnetic moment of the film due to an increase in the 4p–3d hybridization.     

Investigation of stability of ordered manganites

Cation-ordered manganites of the PrBaMn₂O₆ system have been obtained using a two-stage synthesis and characterized with respect to the chemical composition, crystal structure, magnetic and magnetotransport properties, and the stability of the ordered state on heating. The physical properties of the cation ordered PrBaMn₂O₆ manganites obtained using this method significantly differ from the properties of cation disordered Pr_0.50Ba_0.50MnO₃ synthesized by means of the conventional ceramic technology and depend on the degree of ordering of the Pr³⁺ and Ba²⁺ cations. In particular, the cation-disordered Pr_0.50Ba_0.50MnO₃ has a cubic perovskitelike unit cell \((SG = Pm\bar 3m,Z = 1)\), while cation-ordered PrBaMn₂O₆ has a tetragonal unit cell (SG = P4/mmm, Z = 2). Cation states in the system under study are reversible. The cation-ordered PrBaMn₂O₆ state remains stable upon heating in an oxidizing medium (P[O₂] = 1 bar) up to 1300°C. The ordering of the Pr³⁺ and Ba²⁺ cations leads to a significant increase in the critical temperatures of phase transitions. In particular, PrBaMn₂O₆ with the maximum degree of ordering is a metallic ferromagnet with the Curie temperature T_C～320 K, whereas T_C of a fully disordered sample is on the order of 140 K. The samples with intermediate degrees of ordering contain two magnetic phases. Slightly below T_C, all such samples exhibit a metal-insulator transition and a peak of the magnetoresistance, which amounts to approximately 10 and 65% in a magnetic field of 9 kOe for the fully ordered PrBaMn₂O₆ and disordered Pr_0.50Ba_0.50MnO₃, respectively. The results are interpreted in terms of the Goodenough-Kanamori empirical rules for indirect exchange interactions with allowance for the degree of ordering of the Pr³⁺ and Ba²⁺ cations.     

The effect of codopants on spectral-kinetic characteristics of luminescence of scintillation glasses doped with terbium ions

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

Successive structural phase transitions in Pr<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> in the range 10–1120 K

The crystal and magnetic structures of the Pr_0.5Sr_0.5CoO₃ metallic ferromagnet have been studied using neutron diffraction and synchrotron radiation. Successive structural transitions with the reduction of the crystal symmetry from cubic (space group Pm3m) to rhombohedral (\(R\bar 3c\), ～800 K), orthorhombic (Imma, ～300 K) and, then, to triclinic at ～120 K are detected during cooling from 1120 K. The transition from the orthorhombic system to a phase with a lower symmetry is characterized by a sharp change in the anisotropy of the unit cell, which indicates the partial ordering of the e _g orbitals of cobalt. The accompanying change in the interatomic distances and valence angles give rise to an anomaly in the temperature dependence of the magnetic susceptibility at T ≈ 120 K. The ordered magnetic moment μ_Co ≈ 2μ_B corresponds to the assumption of the intermediate spin state of Co³⁺ ions and the mixture of low- and intermediate-spin states of Co⁴⁺ ions.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

Thermoelectric properties of layered ferrocuprates <Emphasis Type="Italic">Ln</Emphasis>BaCuFeO<Subscript>5 + δ</Subscript> (<Emphasis Type="Italic">Ln</Emphasis>= La,Pr, Nd,Sm, Gd-Lu)

The electrical resistivity ρ and the thermopower S of ceramic materials LnBaCuFeO_{5 + δ} (Ln= La, Pr, Nd, Sm, Gd-Lu) are measured in air at temperatures in the range from 300 to 1100 K. All the studied ferrocuprates are p-type semiconductors. The electrical resistivity ρ and the thermopower S of these compounds increase with a decrease in the radius of the Ln ³⁺ cation (with an increase in the number of 4f electrons n in Ln ³⁺). The nonmonotonic behavior of the dependences ρ=f(n) and S=f(n) indicates that the electrical properties of the layered ferrocuprates LnBaCuFeO_{5 + δ} depend on the electronic configuration of the Ln ³⁺ cation. The power factors P calculated for the LnBaCuFeO_{5 + δ} ceramic materials from the experimental values of ρ and S increase with increasing temperature and, at T = 1000 K, reach the maximum values P = 102.0 and 54.1 µW m^?1 K^?2 for Ln = Pr(4f ²) and Sm(4f ⁵), respectively, and become close to each other and equal to 30–35 µW m^?1 K^?2 for Ln = Gd(4f ⁷), Dy(4f ⁹), and Ho(4f ¹⁰).     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> centers in (Cr,Li): Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> synthetic forsterite

Synthetic single crystals of chromium-and lithium-doped forsterite, namely, (Cr,Li): Mg₂SiO₄, are studied using electron paramagnetic resonance spectroscopy. It is revealed that, apart from the known centers Cr³⁺(M1) and Cr³⁺(M2) (with local symmetries C_i and C_s, respectively), these crystals involve two new types of centers with C₁ symmetry, namely, Cr³⁺(M1)′ and Cr³⁺(M2)′ centers. The standard parameters D and E in a zero magnetic field [zero-field splitting (ZFS) parameters expressed in GHz] and principal components of the g tensor are determined as follows: D=31.35, E=8.28, and g=(1.9797, 1.9801, 1.9759) for Cr³⁺(M1)′ centers and D=15.171, E=2.283, and g=(1.9747, 1.9769, 1.9710) for Cr³⁺(M2)′ centers. It is found that the lowsymmetric effect of misalignment of the principal axes of the ZFS and g tensors most clearly manifests itself (i.e., its magnitude reaches 19°) in the case of Cr³⁺(M2)′ centers. The structural models Cr³⁺(M1)-Li⁺(M2) and Cr³⁺(M2)-Li⁺(M1) are proposed for the Cr³⁺(M1)′ and Cr³⁺(M2)′ centers, respectively. The concentrations of both centers are determined. It is demonstrated that, upon the formation of Cr³⁺-Li⁺ ion pairs, the M1 position for chromium appears to be two times more preferable than the M2 position. Reasoning from the results obtained, the R₁ line (the ²E → ⁴A₂ transition) observed in the luminescence spectra of (Cr,Li): Mg₂SiO₄ crystals in the vicinity of 699.6 nm is assigned to the Cr³⁺(M1)′ center.     

Low-temperature time-resolved VUV luminescence spectroscopy of SrF<Subscript>2</Subscript>: Er<Superscript>3+</Superscript> crystals

Time-resolved excitation and emission spectra of SrF₂: Er³⁺ upon selective excitation with synchrotron radiation in the VUV and ultrasoft x-ray ranges at T = 8 K were studied. The VUV luminescence of SrF₂: Er³⁺ derives from high-energy interconfiguration 4f¹⁰5d-4f¹¹ transitions in the Er³⁺ ion. The VUV emission spectrum revealed, in addition to the 164.5-nm band (millisecond-range kinetics), a band at 146.4 nm (with a decay time of less than 600 ps). The formation of excitation spectra for the f-f and f-d transitions in the Er³⁺ ion is discussed.     

Specific features of optical absorption in rare-earth orthoaluminate DyAlO<Subscript>3</Subscript>

Polarization spectra of optical absorption of the 4f-4f transition ⁶ H _15/2 → ⁶ F _3/2 in the rare-earth orthoaluminate DyAlO₃ are theoretically and experimentally studied at the temperature T=78 K. It is shown that the nontrivial character of the anisotropy of the polarization absorption spectra at low temperatures can be explained by the J-J mixing of excited multiplets of the 4f ⁹ configuration of Dy³⁺ ions in a low-symmetry crystal field of the orthoaluminate structure. The energy and wave functions of the Stark sublevels within the excited ⁶ F _5/2 multiplet in the 4f ⁹ configuration of the Dy³⁺ rare-earth ion in the crystal field of C _s symmetry are numerically calculated.     

Observation of high efficiency of Raman scattering in the process of the three-photon ionization of samarium atom

Very high efficiency of Raman scattering on samarium atoms in the process of three-photon ionization has been detected. An intense maximum attributed to the one-photon transition 4f ⁶5d6s ⁹ H ₂ → 4f ⁵5d6s ^{2 7} D ₃° between two excited states is observed in the dependence of the yield of Sm⁺ ions on the laser-radiation frequency. The 4f ⁶5d6s ⁹ H ₂ state is populated owing to the spontaneous Raman scattering 4f ⁶6s ^{2 7} F ₃ + ω ? ν → 4f ⁶5d6s ⁹ H ₂.     

Ds+ → π+ π+ π− decay: The $$1^3 P_0 s\bar s$$ component in scalar-isoscalar mesons

We calculate the processes \(D_s^ + \to \pi ^ + s\bar s\) and D _s ⁺ → π⁺resonance, respectively, in the spectator and W-annihilation mechanisms. The data on the reaction D _s ⁺ → π⁺ρ⁰, which is due to the W-annihilation mechanism only, point to a negligibly small contribution of the W annihilation to the production of scalar-isoscalar resonances D _s ⁺ ?π⁺f₀. As to spectator mechanism, we evaluate the \(1^3 P_0 s\bar s\) component in the resonances f₀(980), f₀(1300), and f₀(1500) and broad state f₀(1200–1600) on the basis of data on the decay ratios D _s ⁺ ?π⁺f₀/(D _s ⁺ ?π⁺_θ). The data point to a large \(s\bar s\) component in the \(f_0 (980):40 \lesssim s\bar s \lesssim 70\% \). Nearly 30% of the \(1^3 P_0 s\bar s\) component flows to the mass region 1300–1500 MeV, being shared by f₀(1300), f₀(1500), and broad state f₀(1200–1600): the interference of these states results in a peak near 1400 MeV with the width around 200 MeV. Our calculations show that the yield of the radial-excitation state\(2^3 P_0 s\bar s\)is relatively suppressed, \({{\Gamma (D_s^ + \to \pi ^ + (2^3 P_0 s\bar s))} \mathord{\left/ {\vphantom {{\Gamma (D_s^ + \to \pi ^ + (2^3 P_0 s\bar s))} {\Gamma (D_s^ + \to \pi ^ + (1^3 P_0 s\bar s))}}} \right. \kern-\nulldelimiterspace} {\Gamma (D_s^ + \to \pi ^ + (1^3 P_0 s\bar s))}} \lesssim 0.05\).     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

Spectral and luminescence properties of gadolinium gallium garnet epitaxial films doped with terbium

Gadolinium gallium garnet single-crystal films containing terbium are grown through liquid-phase epitaxy from a supercooled solution melt in the PbO-B₂O₃ system. The optical absorption spectra in the wavelength range 0.2–10.0 μm and the luminescence spectra excited by synchrotron radiation with energies in the range 3.5–30.0 eV are investigated at temperatures of 10 and 300 K. It is revealed that the optical absorption spectra contain an absorption band with the maximum at a wavelength λ ≈0.260 μm, which corresponds to the spin-allowed electric dipole transition between the electronic configurations 4f ⁸(⁷ F ₆) → 4f ⁷(⁸ S)5d of the Tb³⁺ ions. The narrow low-intensity absorption bands attributed to the 4f → 4f transitions from the ⁷ F ₆ ground level to the ⁷ F _0–5 multiplet levels of the Tb³⁺ ions are observed in the wavelength range 1.7–10.0 μm. In the luminescence spectra measured at a temperature of 10 K, the highest intensity is observed for a band with the maximum at a wavelength λ ≈ 0.544 μm, which is associated with the ⁵ D ₄ → ⁷ F ₅ radiative transition in the Tb³⁺ ion.     

Quark microscopic picture for vector and pseudoscalar mesons in the nucleon and their quasielastic knockout by high-energy electrons

A technique for projecting a multiquark wave function in the microscopic model of a ³P⁰ scalar fluctuation onto the virtual-decay channels N → N + ρ and N → N + π is formulated (at a more general level for the latter than previously). The amplitude for the electromagnetic transition ρ + γ _T ^* → π in electron-induced quasielastic rho-meson knockout followed by rho-meson conversion to a pion is considered. Theoretical results obtained in this way are contrasted against available experimental data, and reasonable agreement is found for cross-section values. This confirms a universal character of the ³P₀ model. The precision of relevant experiments is as yet insufficient for comparing the momentum distribution of the rho meson from the channel N → N + ρ with its theoretical counterpart.     

Many-electron model of band structure and metal-insulator transition under pressure in FeBO<Subscript>3</Subscript>

A many-electron model is proposed for the band structure of FeBO₃ with regard to strong electron correlations in the d⁴, d⁵, and d⁶ configurations. Under normal conditions, FeBO₃ is characterized by a dielectric charge-transfer gap in the strong correlation regime U?W. With increasing pressure, not only does the d-band W width grow but simultaneously the effective Hubbard parameter U_eff sharply drops, which is due to the crossover of high-spin and low-spin ground state terms of the Fe²⁺, Fe³⁺, and Fe⁴⁺ ions. It is predicted that a transition from the semiconducting antiferromagnetic state to the metallic paramagnetic state will occur in the high-pressure phase with increasing temperature.