Crystal structure phase separation in anion-deficient La0.70Sr0.30MnO3 − δ manganite system

The crystal structure of anion-deficient La_0.70Sr_0.30MnO_{3 ? δ} manganite powders (δ = 0, 0.10, 0.15, 0.20) has been investigated at room temperature by the neutron diffraction method using a high-resolution Fourier diffractometer. The structure data have been refined by the Rietveld method. The crystal structures of the stoichiometric La_0.70Sr_0.30MnO₃ and anion-deficient La_0.70Sr_0.30MnO_2.90 manganites are satisfactorily described by the rhombohedral space group R $\bar 3$ c. A small amount of the non-perovskite MnO phase (space group Fm $\bar 3$ m) has been found for the anion-deficient La_0.70Sr_0.30MnO_2.90 sample. It has been found that the anion-deficient La_0.70Sr_0.30MnO_2.85 sample consists of two perovskite phases described by space groups R $\bar 3$ c and I4/mcm and the MnO phase (space group Fm $\bar 3$ m). The crystal structure of the anion-deficient La_0.70Sr_0.30MnO_2.80 sample is described by one perovskite phase with space group I4/mcm. The volume fraction of the MnO phase is ?1% for all anion-deficient samples. Oxygen vacancies in the anion-deficient La_0.70Sr_0.30MnO_{3 ? δ} manganite system stimulate the structure phase separation at 293 K.     

Cation distribution of the system Zn1−xCoxFeMnO4 by x-ray,electrical conductivity and Mössbauer studies

Structural, electrical and Mössbauer studies were carried out for the system Zn_1?xCo _x Fe MnO₄. It is observed that forx?0.6, the ionic configuration of the system is Zn _1?x ²⁺ Mn _x ²⁺ [Co _x ³⁺ Mn _1?x ³⁺ Fe³⁺]O ₄ ^2? and forx?0.8 Fe³⁺ ions occupy tetrahedral site also. On the basis of electrical and Mössbauer studies a probable valence distribution of CoMnFeO₄ has been suggested. All the compounds showed positive values of thermoelectric coefficient and electrical conduction takes place by a hopping mechanism. Activation energy and thermoelectric coefficient values decreased with decrease in concentration of Zn²⁺ ions. The compounds possess low mobility values varying between 10^?7 and 10^?9 cm²/V sec.     

Concentration-dependent structural transition in the La0.70Sr0.30MnO3−δ system

The crystal structure of anion-deficient La_0.70Sr_0.30MnO_3?δ manganites (δ = 0, 0.10, 0.15, and 0.20) has been studied by powder neutron diffraction at room temperature. The crystal structures of the stoichiometric La_0.70Sr_0.30MnO₃ and anion-deficient La_0.70Sr_0.30MnO_2.90 samples are satisfactorily described by the rhombohedral R $\bar 3$ c space group. The anion-deficient La_0.70Sr_0.30MnO_2.85 sample separates into two perovskite phases with the R $\bar 3$ c and I4/mcm space groups. The crystal structure of La_0.70Sr_0.30MnO_2.80 cannot be described by a single perovskite phase in the I4/mcm space group. It is found that the clustering of oxygen vacancies is the cause of structural phase separation at 293 K in anion-deficient La_0.70Sr_0.30MnO_3?δ manganites.     

Luminescence of Sc3+ and La3+ isoelectronic impurities in Lu3Al5O12 single-crystal films

The time-resolved luminescence and luminescence excitation spectra, and luminescence decay kinetics at 8 and 300 K of Lu₃A₁₅O₁₂ (LuAG) single-crystal films doped with Sc³⁺ and La³⁺ isoelectronic impurities and excited by synchrotron radiation are investigated. It is established that the La³⁺ isoelectronic impurity in the ?ub;c?ub; positions of the garnet lattice forms La _Lu ³⁺ luminescence centers emitting in the band with λ_max = 280 nm and the decay time of the main component τ = 300 ns at 300 K. The Sc³⁺ isoelectronic impurity located in the ?ub;c?ub; and (a) positions of the LuAG lattice forms two luminescence centers, Sc _Lu ³⁺ and Sc _Al ³⁺ , emitting in the bands with λ_max = 290 nm and τ = 240 ns and λ_max = 335 nm and τ = 375 ns, respectively, at 300 K. It is shown that the luminescence excitation of the La³⁺ and Sc³⁺ isoelectronic impurities in LuAG single-crystal films occurs through radiative decay of excitons localized near La _Lu ³⁺ , Sc _Lu ³⁺ , and Sc _Al ³⁺ centers. The energies of formation of these excitons are determined to be 6.8, 6.88, and 7.3 eV, respectively. It was found that the excited state of the excitons genetically related to the La _Lu ³⁺ , Sc _Lu ³⁺ , and Sc _Al ³⁺ enters has two radiative levels with different transition probabilities. This configuration leads to the presence of fast (2.3–8.4 ns) and slow (150–375 ns) main components in the luminescence of the centers formed by isoelectronic impurities in garnets.     

NQR study of spin-freezing in superconducting La2−x Sr x CuO4: the example ofx = 0.06

Nuclear quadrupole resonance (NQR)¹³⁹La and⁶³Cu spin-lattice relaxation rateT ₁ ^t-1 measurements in a La_1.94Sr_0.06CuO₄ single crystal are described. Slowing-down of Cu²⁺ spin fluctuations is evidenced through a dramatic increase of¹³⁹ T ₁ ^?1 on cooling. While the onset of diamagnetism occurs atT _c = 8 K,¹³⁹ T ₁ ^?1 has a peak atT _g ? 5 K, when the characteristic frequency of magnetic fluctuations reaches the NQR frequencyv _Q ? 9 MHz. In agreement with a number of previous studies, these results show that the so-called “cluster spin-glass” phase persists in the superconducting regime. Issues concerning the coexistence of the two phases are discussed.     

Electron paramagnetic resonance and optical spectroscopy of K3Na(CrO4)2 ferroelastics activated by MnO 4 2− molecular impurity ions

Crystals of a proper ferroelastic K₃Na(CrO₄)₂ containing molecular impurity ions MnO ₄ ^2? are studied using electron paramagnetic resonance (EPR) and optical spectroscopy. The EPR spectrum of the Mn⁶⁺ ion contained in the molecular impurity ion MnO ₄ ^2? is identified at low temperatures (T ≤ 20 K). The intensity of this spectrum decreases unusually fast as the temperature increases. A broad IR luminescence band with a vibronic structure well resolved at a temperature of 8 K is revealed. Theoretical treatment of the Mn⁶⁺ ion involved in the molecular impurity ions MnO ₄ ^2? of the K₃Na(CrO₄)₂ ferroelastic crystal suggests that an important role in this case is played by the pseudo-Jahn-Teller. The pseudo-Jahn-Teller effect offers an explanation for the appearance of a fine structure in the vibronic replicas in the luminescence spectrum, on the one hand, and accounts for the fast decrease in the intensity of the EPR spectrum of K₃Na(CrO₄)₂: MnO ₄ ^2? with increasing temperature, on the other.     

Phase transitions in manganites with substitution of divalent ions for manganese

Experimental data are presented for the position of phase boundaries “orthorhombic-rhombohedral structure” and “semiconductor-metal” in manganites of La_{1 ? c + x} Sr _{c ? x} ²⁺ Mn_{1 ? x} Me _x ²⁺ O_{3 + γ} (Me = Mg, Zn, Ni) systems depending on the concentration of substituting divalent cations (0.15 ≤ c ≤ 0.35; 0.025 ≤ x ≤ 0.100).     

Laser Raman spectra of mixed crystals of [(NH4)1−x Kx]2 SO4

The Raman spectra of mixed crystals of [(NH₄)_1?x K _x ]₂ SO₄ in the region 50–3400 cm^?1 at 293 K and below 223 K have been reported. At room temperature 293 K, as the concentration of K⁺ ion increases in the crystal up to 50%, the frequencies of the totally symmetric vibrations of SO ₄ ^2? and NH ₄ ⁺ ions increase and thereafter the frequency of SO ₄ ^2? vibration decreases and attains the value in K₂SO₄. This change in frequency up to 50% of potassium concentration is due to the breaking of hydrogen bonds of the type N-H...O. The behaviour of Raman intensities of A _g (v ₁) mode of SO ₄ ^2? for various concentrations (x=0, 0·03, 0·11, 0·5, 0·85) suggest that the phase transition changes from first order type to one of second order. The phase transition in mixed crystals of [(NH₄)_1?x K _x ]₂ SO₄ can be a cooperative phenomenon arising from a coupling between (NH₄)⁺ ions through hydrogen bonds with the distorted SO ₄ ^2? ions in the low temperature phase.     

Electrical and magnetic properties of La0.67Ba0.33Mn1−x (Me) x O3 perovskite manganites: case of manganese substituted by trivalent (Me = Cr) and tetravalent (Me = Ti) elements

The effects of non-magnetic Ti⁴⁺ substitution on the structural, electrical and magnetic properties of La_0.67Ba_0.33Mn_1?x Ti _x O₃ (0≤x≤0.1) are investigated and compared to those existing in La_0.67Ba_0.33Mn_1?x Cr _x O₃ (magnetic Cr³⁺). The structural refinement by the Rietveld method revealed that Ti-doped samples crystallize in the cubic lattice with space group $\mathrm{Pm}\bar{3}\mathrm{m}$ , while samples with Cr crystallize in the hexagonal setting of the rhombohedral $\mathrm{R}\bar{3}\mathrm{C}$ space group for identical contents of dopant. The most relevant structural features are an increase of the lattice parameters, of the cell volume and of the inter-ionic distances with increasing Ti doping level. Both series of samples show a decrease of the paramagnetic–ferromagnetic transition temperature when the amount of chromium or titanium increases. Transport measurements show that when increasing the metal doping, the resistivity increases whereas the metallic behavior of the parent compound La_0.67Ba_0.33MnO₃ is destroyed. For a substitution higher than 5 at.% of Ti and 10 at.% of Cr, the samples exhibit a semiconducting behavior in the whole range of temperature, for which the electronic transport can be explained by variable range hopping and/or small polaron hopping models.     

Spin-reorientation transition at isoelectronic substitution in double-layer manganites (La1−z Prz)1.2Sr1.8Mn2O7

The transport, magnetic, and thermal properties of single crystal double-layer manganites of the Ruddlesden-Popper series (La_1?z Pr_z)_1.2Sr_1.8Mn₂O₇ (z=0.1 or 0.4) were studied. The compounds exhibit the colossal negative magnetoresistance effect in the region of a transition into a ferromagnetic state. Upon the isoelectronic substitution of Pr³⁺ for La³⁺, the Curie temperature decreases, while the easy magnetization axis rotates from the ab plane to the c axis. The observed effect is related to a change in the occupancy of $d{x^2-y^2} $ and $d{3z^2-r^2} $ orbitals as a result of stretching of the MnO₆ octahedra.     

Origin of the electron spin resonance signal in the manganites: from polarons to phase separation

In the manganites L_1?xM_xMnO₃ (L = La, Nd, Pr, …; M = Sr, Ba, Ca, …), the doping concentration introduces a mixed valence (Mn³⁺, Mn⁴⁺) which governs the magnetic and electric properties of the compound. Mn³⁺ (S = 2) is scarcely observed in electron spin resonance (ESR). In contrast, Mn⁴⁺ (S = 3/2), is a good ESR probe. However, X-band measurements show an enhanced Mn⁴⁺ susceptibility, which is the signature of some kind of coupling of the Mn⁴⁺ ions with the Mn³⁺ ions, but its exact nature is still controversial. We present multifrequency ESR experiments (9–385 GHz) obtained on different systems (La_1?δMnO₃, La_1?xMnO₃, La_1?xCa_xMnO₃, and Nd_1?xCa_xMnO₃) in the low-concentration range (0 <x< 0.33). In the paramagnetic regime, the Mn³⁺ spectrum cannot be observed because of fast relaxation. The signal arises from polarons, whose size, temperature and magnetic field dependences vary with M andx. The single line observed in the metallic compound evolves towards a double-peak structure visible at high frequency in La_0.97MnO₃. Its evolution with temperature below the magnetic transition reveals the presence of manganese ions in a different magnetic environment, i.e., phase separation. The magnetic order of the separated phase is not ferromagnetic. It is a more complex order, which depends substantially on the nature of the cation M.     

Spin states of cobalt and the thermodynamics of Sm1 − x Ca x CoO3 − δ solid solutions

In the rare-earth SmCoO₃ perovskite, Co³⁺ ions at low temperatures appear to be in the low-spin state with S = 0, t _2g ² e _g ⁰ . If Ca²⁺ ions partially substitute Sm³⁺ ions, oxygen deficient Sm_{1 ? x} Ca _x CoO_{3 ? δ} solid solutions with δ = x/2 appear. The oxygen deficiency leads to the formation of pyramidally coordinated cobalt ions Co _pyr ³⁺ in addition to the existing cobalt ions Co _oct ³⁺ within the oxygen octahedra. Even at low temperatures, these ions have a magnetic state, either S = 1, t _2g ⁵ e _g ¹ or S = 2, t _2g ⁴ e _g ² . At low temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _pyr ³⁺ ions. Owing to the characteristic features of the crystal structure of the oxygen deficient perovskite, these ions form a set of nearly isolated dimers. At high temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _oct ³⁺ ions, which exhibit a tendency to undergo the transition from the S = 0, t _2g ⁶ e _g ⁰ state to the S = 1, t _2g ⁵ e _g ¹ or S = 2, tt _2g ⁴ e _g ² state. In addition, the magnetization and specific heat of the solid solutions under study include the contribution from the rare-earth subsystem, which undergoes a magnetic ordering at low temperatures.     

X-ray study of some spinels containing gallium and manganese

The ternary oxides CrMnGaO₄, NiMnGaO₄, CuMnGaO₄ and ZnMnGaO₄, crystallize in the cubic spinel structure with lattice parametera=8.41±0.02 Å, 8.34±0.02 Å, 8.36±0.02 Å and 8.32±0.02 Å, respectively. The oxidation state of manganese in these spinels was determined x-ray spectroscopically. The site distribution was determined from the structural properties and calculated site preference energies of cations in the lattice. The ionic structures were found to be Ga³⁺ [Mn²⁺ Cr³⁺] O ₄ ^2? . Ga³⁺ [Cu²⁺ Mn³⁺] O ₄ ^2? , Mn²⁺ [Ga³⁺ Ni³⁺] O ₄ ^2? and Zn²⁺ [Mn³⁺ Ga³⁺] O ₄ ^2? .     

Classical Kepler-Coulomb problem on SO(2, 2) hyperboloid

In the present work, the problem of the motion of the classical particle in the Kepler-Coulomb field in three-dimensional hyperbolic space H ₂ ² : z ₂ ⁰ + z ₂ ¹ ? z ₂ ² ? z ₂ ³ = R ² is solved in the framework of Hamilton-Jacobi equation. The requirements for the existence of bounded motion of particle are formulated. The equation of the trajectory of particle is obtained, and it is shown that all the finite trajectories are closed. It is also demonstrated that under the certain values (zero or negative) of the separation constant A the fall of the particle onto the center takes place.     

Ionization and dissociative ionization of methane molecules

A technique for mass-spectrometric investigation of the yield of positive ions produced by direct and electron-impact dissociative ionization of methane molecules is described, and respective experimental data are presented. Doubly charged C ₂ ⁺ , CH ₃ ²⁺ , and CH ₄ ²⁺ ions, as well as singly charged D ₂ ⁺ , CD ₃ ⁺ , and CD ₄ ⁺ ions, are detected in the mass spectrum of a methane molecule at electron energy U _e = 90 eV for the first time. From ionization efficiency curves, the ionization energy of the parent molecule and the appearance energy of fragment ions are determined. The ionization energy of the CH₄ molecule is found to be 12.62 ± 0.20 eV. Electron-molecular reactions that may take place when a low-energy electron beam interacts with a methane molecule are analyzed. The ionization process and the formation of methane molecule fragments are studied.     

The Kepler-Coulomb problem on SO(2, 2) hyperboloid

In this note the Kepler-Coulomb problem in hyperbolic space H ₂ ² : z ₀ ² + z ₁ ² ? z ₂ ² ? z ₃ ² = R ² is discussed.     

Low energy π-π resonances in the Veneziano model

We attempt to impose elastic unitarity on the forward π-π scattering using the Veneziano Amplitude together with a crossing symmetric subtraction term as an input. TheN/D method is used and thep, ? mesons are interpreted as CDD poles. The self consistency requirement led to the evalutation of the low energy parameters and theS andP-wave phase shifts. The values of the scattering lengths obtained area ₀ ⁰ =0.084m _π ^?1 ,a ₂ ⁰ =?0.024m _π ^?1 ,a ₁ ¹ =0.047m _π ^?3 .     

Measurement of theg-factor of the 4 1 + -state of202Pb

Theg-factor of the 4 ₁ ⁺ -state of²⁰²Pb was investigated by the IPAC-technique. Inspite of the long half-life, which was measured as:T _1/2(4 ₁ ⁺ -state)=1.97(2)ns and the strong applied external magnetic field of 95.0 kG no rotation of the 787 keV-(422keV)-961 keVγ-γ angular correlation could be observed. Theg-factor must therefore be very small. A computer fit gave the limits:g(4 ₁ ⁺ -state)=+0.002(4). This smallg-factor can be understood by the assumption of an accidental cancellation of a positive contribution by the main [f _5/2 ² ]₄-configuration and several negative contributions by admixtures of all other possible two neutron configurations.     

Untersuchung der vier ersten angeregten Zustände des6Li-Kernes durch Elektronenstreuung

Inelastic electron scattering cross sections were measured for energies below 60 MeV and momentum transfersq between 0.2 and 0.6 fm^?1. Ground state radiative widths Γ _γ ⁰ and transition radiiR _tr were deduced. 2.18 MeV: Γ _γ ⁰ (E2)=(4.40±0.34) · 10^?4 eV,R _tr=(4.28±0.39)fm; 3.56MeV: Γ _γ ⁰ (M1)=(8.31±0.36)eV,R _tr=(2.90±0.10)fm; 4.27 MeV: Γ _γ ⁰ (E2)=(5.4±2.8) · 10^?3 eV,R _tr=(3.4±1.2) fm. The excitation of the 5.37 MeV level shows a transverse angular dependence.