Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.     

Effect of high pressure on the crystal and magnetic structure and on the raman spectra in Pr<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> manganite

The crystal and magnetic structure and the Raman spectra in Pr_0.7Ba_0.3MnO₃ manganite have been studied by the neutron diffraction technique at pressures up to 5 GPa as well as by the X-ray diffraction and Raman spectroscopy at pressures up to 30 GPa. The pressure dependence is determined for the lattice parameters, unit cell volume, Mn-O bond lengths in the orthorhombic structure of the Imma symmetry, and bending and stretching vibration modes for oxygen octahedra. In the low-temperature range at pressure P = 1.9 GPa, the magnetic transition from the initial ferromagnetic (FM) ground state (T _C = 197 K) to the A-type antiferromagnetic (AFM) state (T _N = 153 K) has been revealed. The FM and AFM phases coexist at pressures up to 5.1 GPa and exhibit negative and positive values of the pressure coefficient for the Curie and Néel temperature, respectively (dT _C/dP = −2.3 K/GPa and dT _N/dP = 8 K/GPa). The pressure dependence of the Curie temperature in Pr_0.7Ba_0.3MnO₃ differs drastically from that observed in other manganites of nearly the same composition with the orthorhombic Pnma and rhombohedral R[`3]cR\bar 3c structures, where the FM phase is characterized by the positive values of dT _C/dP. The structural mechanisms of these phenomena are discussed.     

Structure and magnetization studies of Nd0.5−xPrxSr0.5MnO3 system

The structural and magnetic properties of Nd_0.5−xPr_xSr_0.5MnO₃ (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) system have been investigated. With the substitution of Pr in Nd_0.5Sr_0.5MnO₃, it shows a gradual structure transformation from the Imma orthorhombic symmetry to the tetragonal I4/mcm phase, and the crystallographic transition remains incomplete, even in Pr_0.5Sr_0.5MnO₃. A large bifurcation between zero-field-cooled (ZFC) and field-cooled (FC) susceptibility has been observed below Curie temperature (T_C), which is characteristic of coexistence of ferromagnetism (FM) and antiferromagnetism (AFM) at low temperature region. The magnetization of Pr_0.5Sr_0.5MnO₃ is larger than that of Nd_0.5Sr_0.5MnO₃, while Nd_0.5Sr_0.5MnO₃ with more CE-type AFM shows larger magnetization than Nd_0.3Pr_0.2Sr_0.5MnO_3, which mixed with CE-type (majority) and A-type (minority) AFM at low temperature, indicating that the magnetization of Nd_0.5−xPr_xSr_0.5MnO₃ system is affected by A-site disorder combined with orbital ordering of A-type AFM and CE-type AFM.     

Pressure-induced structural transformations,orbital order and antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

High pressure evolution of structural, vibrational and magnetic properties of La_0.75Ca_0.25MnO₃ was studied by means of X-ray diffraction and Raman spectroscopy up to 39 GPa, and neutron diffraction up to 7.5 GPa. The stability of different magnetic ground states, orbital configurations and structural modifications were investigated by LDA + U electronic structure calculations. A change of octahedral tilts corresponding to the transformation of orthorhombic crystal structure from the Pnma symmetry to the Immaone occurs above P ~ 6 GPa. At the same time, the evolution of the orthorhombic lattice distortion evidences an appearance of the e _g d _{x² ? z²} orbital polarization at high pressures. The magnetic order in La_0.75Ca_0.25MnO₃ undergoes a continuous transition from the ferromagnetic 3D metallic (FM) ground state to the A-type antiferromagnetic (AFM) state of assumedly 2D pseudo-metallic character under pressure, that starts at about 1 GPa and extends possibly to 20–30 GPa.     

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.     

Magnetic phase transitions in the iron-doped Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>Mn<Subscript>1−<Emphasis Type="Italic">y</Emphasis></Subscript>Fe<Subscript>y</Subscript>O<Subscript>3</Subscript> manganites at high pressures

The atomic and magnetic structures of the iron-doped Pr_0.7Ca_0.3Mn_1?yFe_yO₃ manganites (y=0, 0.1) have been studied at high pressures of up to 4 GPa in the temperature range 16–300 K. At normal pressure, Pr_0.7Ca_0.3MnO₃ undergoes a phase transition from the paramagnetic to an antiferromagnetic (AFM) state of the pseudo-CE type and Pr_0.7Ca_0.3Mn_0.9Fe_0.1O₃ undergoes a phase transition from the paramagnetic to the ferromagnetic state at low temperatures. Partial substitution of Mn atoms by Fe brings about a noticeable decrease in the average magnetic moment per atom. A new A-type AFM state was observed to form in Pr_0.7Ca_0.3MnO₃ at a pressure P≈2.2 GPa and in Pr_0.7Ca_0.3Mn_0.9Fe_0.1O₃ at 2.7 GPa. This phenomenon may originate from the anisotropy in the compressibility, which causes uniaxial contraction of the oxygen octahedra MnO₆ in the structure and provides favorable conditions for the formation of an A-type AFM state. The structural parameters obtained were used to calculate the pressure dependence of bandwidth in the compounds under study.     

Lattice dynamics and baric behavior of phonons in Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> crystals at high hydrostatic pressures

A theoretical model based on long-range dispersion corrections of the charge density functional is proposed for model Hg₂Cl₂ calomel crystals, typical representatives of molecular inorganic compounds where the intermolecular interaction is found to play an important role. This model successfully describes the electronic state and the phonon spectrum of the above crystal, predicts the earlier unstudied phase transition at high hydrostatic pressure. Study of the baric behavior of the phonon spectrum with Raman spectroscopy observes the soft mode in the low-symmetry orthorhombic phase with the frequency softening as the pressure rises. Pressures above 9 GPa considerably transform the Raman spectra, indicating a structural phase transition.     

Structural and phonon dynamical properties of perovskite manganites: (Tb, Dy, Ho)MnO3

A shell model has been used to study the structure, phonon dynamics and phase coexistence of perovskite manganites RMnO₃ (R=Tb, Dy, Ho). The calculated crystal structure, Raman and IR frequencies and specific heats are found to be in good agreement with the available experimental data. The phonon density of states, elastic constants, elastic stiffness, shear constants and phonon dispersion curves have been computed for these manganites. A zone center imaginary A_u mode is revealed in these phonon dispersion curves, which indicates the occurrence of the metastability of the perovskite phase. The Gibbs free energy values calculated as a function of temperature and pressure for RMnO₃ in the orthorhombic phase, when compared with those of the hexagonal phase, reveal the possibility of coexistence of these two phases in the present multiferroic manganites under ambient conditions.     

Temperature dependence of infrared conductivity of manganites (x = 0, 0.05 and 0.2)

The temperature dependence of the reflectivity spectra of three manganites ceramics with compositions Pr_0.7Ca_0.3MnO₃, Pr_0.7Ca_0.25Sr_0.05MnO₃ and Pr_0.7Ca_0.1Sr_0.2MnO₃ has been investigated by infrared reflectivity spectroscopy in the wave number range 0.005-1.1 eV. The compound Pr_0.7Ca_0.25Sr_0.05MnO₃ which shows the largest conductivity jump at the ferromagnetic-paramagnetic phase transition has been studied in details. The optical conductivity of this compound is deduced from the best fit to reflectivity spectra of a “double-damping Drude” model, itself derived from the factorized form of the dielectric function. Excellent agreement with Kramers-Kronig transformation is reported. The model allows in particular to discriminate the contributions to the optical conductivity of trapped charges (polarons) and mobile charge carriers. Received 20 July 1999 and Received in final form 15 October 1999     

Raman scattering in InN films and nanostructures

Studies of lattice dynamics devoted to wurtzite InN are presented. Raman scattering experiments on both InN thin films and nanometric islands grown by Metal–Organic Vapor Phase Epitaxy (MOVPE) were performed at room temperature. From the Raman spectra recorded from InN films under hydrostatic pressure up to 13 GPa, linear pressure coefficients and the corresponding Grüneisen parameters for both E₂ and A₁(LO) phonons were extracted for the wurtzite structure up to 11 GPa, close to the starting pressure of the hexagonal to rock-salt phase transition of InN. Spectra at higher pressure suggest that InN undergoes a gradual phase transition, and the reverse transition exhibits a strong hysteresis effect during the downstroke. Then, we discuss recent results on large single InN islands grown on GaN buffer layers, obtained by spatially resolved micro-Raman measurements. The magnitude of the residual strain is estimated, using a recent determination of phonon deformation potentials. It is found to vary linearly as a function of island height.     

Study of crystal and magnetic structures of manganite Pr<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressure

The crystal and magnetic structures of manganite Pr_0.7Ba_0.3MnO₃ have been studied at high pressures of up to 5.1 GPa and temperatures from 10 to 300 K by means of the neutron diffraction. At normal pressure and a temperature T _C = 200 K, a ferromagnetic state forms in Pr_0.7Ba_0.3MnO₃. At high pressures P ≥ 1.9 GPa and T < T _N ≈ 153 K, a new antiferromagnetic state of A-type have been observed. Under high pressure, the Curie temperature T _C increases with the characteristic quantity dT _C/dP ≈ 2.4 K/GPa. A possible reason for the appearance of an A-type antiferromagnetic phase in Pr_0.7Ba_0.3MnO₃ at high pressures may be anisotropic uniaxial compression of oxygen octahedra along the b axis of the orthorhombic structure.     

Structural properties and Raman spectroscopy of orthorhombic (Eu1−xPrx)0.6Sr0.4MnO3 (0≤x≤1.0)

The effect of Pr doping on structural properties and room temperature Raman spectroscopy measurements is investigated in manganites (Eu_1−xPr_x)_0.6Sr_0.4MnO₃ (0≤x≤1.0) with fixed carrier concentration. The result of the Rietveld refinement of x-ray powder diffraction shows that these compounds crystallize in an orthorhombic distorted structure with a space group Pnma. It is evident that, with increasing Pr substitution, three types of orthorhombic structures can be distinguished. The phonon frequencies of the three main peaks, in room temperature Raman-scattering measurements, have been discussed together with their structural characteristics, such as bond-length, bond-angles, and the change of orthorhombic structure type. With the increase of Pr content, the mode at 491  cm⁻¹ also shows a corresponding change. A step effect becomes evident, which seems to indicate the close dependence between the frequency shift of this mode and the change in crystal symmetry. This further supports the notion that the mode at 491  cm⁻¹ is closely correlated with the Jahn–Teller distortion. Moreover, we have found that the lowest frequency peak (assigned as an A_1g phonon mode) depends linearly on the tolerance factor t.     

Photo-and pressure-induced transformations in the linear orthorhombic polymer of C<Subscript>60</Subscript>

Stability of the linear orthorhombic polymer of C₆₀ under pressure and laser irradiation is studied by Raman scattering and X-ray diffraction measurements. The Raman spectrum at ambient pressure remains unchanged, in the time scale of the experiment, up to an intensity of 3200 W/cm² of the 514.5 nm line of an Ar⁺ laser, but irreversible changes are observed at higher intensities. The Raman spectra recorded at increased pressure show similar irreversible changes even at the laser intensity as low as 470 W/cm². The X-ray diffraction and Raman measurements of the pressure-treated samples, performed after pressure release, show that the nonirradiated material does not exhibit any changes in the crystal structure and phonon spectra. This behavior indicates a pressure-enhanced photo-induced transformation to a new polymeric phase characterized by a Raman spectrum that differs from those of the other known polymeric phases of C₆₀. The Raman spectra of the phototransformed linear orthorhombic polymer of C₆₀ were measured at a pressure of up to 29 GPa. The pressure dependence of the Raman mode frequencies show singularities near 4 GPa and 15 GPa, respectively, related to a reversible phase transition and an irreversible transformation to a metastable disordered phase. The diffuse Raman spectrum of the disordered phase does not exhibit substantial changes with an increase in pressure up to 29 GPa. The high-pressure phase transforms to a mixture of pristine and dimerized C₆₀, after pressure release and exposure to ambient conditions for 30 h. The text was submitted by the authors in English.     

Phase transitions induced by a strong magnetic field in electron-doped manganites

The magnetic and magnetoelastic properties of single crystals of electron-doped rare-earth manganites La_1?x Sr _x MnO₃ are studied. Phase transitions from the A-type antiferromagnetic phase to the C-type anti-ferromagnetic phase in a strong magnetic field are revealed in La_1?x Sr _x MnO₃ manganites with a strontium content x = 0.65. A similar phase transition is observed in manganites with a strontium content x = 0.8, at which the La_0.2Sr_0.8MnO₃ manganite is assumed to transform from the C-type antiferromagnetic phase to the G-type antiferromagnetic phase.     

High pressure effect on the crystal and magnetic structure of Pr0.1Sr0.9MnO3 manganite

The crystal and magnetic structure of Pr_0.1Sr_0.9MnO₃ manganite has been studied by the neutron diffraction at high pressures up to 5 GPa in the temperature range 10?C295 K. At normal pressure and decreasing temperature the appearance of the C-type (T _N = 220 K) and G-type (T _N = 180 K) antiferromagnetic states occurs, which is accompanied by a structural phase transition from the cubic structure (Pm $ \bar 3 $ m space group) to the tetragonal structure (I4/mcm space group). It is shown that the temperature of the transition to the C-type antiferromagnetic phase increases with pressure with the pressure coefficient dT _N/dP = 4.0(5) K/GPa and the temperature of the transition to the G-type antiferromagnetic phase weakly depends on pressure.     

Size of the interpolated cation and hole carrier density: two key parameters for the optimisation of colossal magnetoresistive properties of Pr-based manganites

The exploration of the magnetic and transport properties of four series of manganese perovskites, Pr_0.7Ca_0.34?xA_xMnO_3?δ (A=Sr, Ba), Pr_0.7?xLa_xCa_0.3 MnO_3?δ and Pr_0.66Ca_0.34?x Sr_xMnO_3?δ has allowed four phases with colossal magnetoresistive (CMR) properties to be isolated: Pr_0.7Ca_0.25Sr_0.025MnO_3?δ and Pr_0.66Ca_0.26Sr_0.08MnO_3?δ that exhibit a variation of resistance of 2.5. 10⁷% and 10⁹% at μ₀ H=5 T for T=88 K and 50 K respectively, Pr_0.58La_0.12Ca_0.3 MnO_3?δ that exhibits a variation of 6.10⁶% for μ₀ H=5 T at T=80 K and Pr_0.7Ba_0.025Ca_0.275MnO_3?δ for which a resistance variation of 5.10⁹%, at T=50 K, for μ₀ H=5 T is evidenced. for each compound of this series except the barium phase, one observes that the temperature T_max, which corresponds to the resistance maximum on the R(T) curves in zero magnetic field, increases dramatically as the mean size of the interpolated cations increases, and that the CMR effect correlatively decreases dramatically. The comparison of the two series Pr_0.7Ca_0.3?xSr_xMnO_3?δ and Pr_0.66Ca_0.34?xSr_xMnO_3?δ shows also the crucial role of the hole carrier density: for a same mean ionic radius of the interpolated cation T_max is decreased of about 50 K by introducing 0.034 hole per Mn mole.     

Structure and dynamics of the pure and mixed fluorites <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Ca,Sr, Ba,and Pb)

The structure and dynamics of the crystal lattice of MeF₂ fluorites (Me = Ca, Sr, Ba, and Pb) under external hydrostatic compression (0–3.5 GPa) are calculated within the shell model in the pair potential approximation. The first-order structural phase transition from the cubic to the orthorhombic phase in these crystals under pressure is investigated. The effect of chemical pressure on the BaF₂ crystal is analyzed by the simulation of mixed crystals, namely, Ba_1?xCa_xF₂ and Ba_1?xSr_xF₂. It is demonstrated that the supercell method, as applied to the simulation of mixed crystals, results in a lower lattice energy per formula unit as compared to the lattice energy obtained by the virtual-crystal method.     

Neutron diffraction evidence for an antiferromagnetic ordering in the CMR manganites Pr0.7Ca0.3−xSrxMnO3

A powder neutron diffraction study on the giant magnetoresistive oxides Pr_0.70Ca_{0.3−xSrxMnO3} has been performed versus temperature for x = 0.1 and 0.05. The first one, Pr_0.7Ca_0.3Sr_0.1MnO₃, exhibits the smaller R₀/R_H ratio (100 at 100 K) and evidences a transition from paramagnetic to ferromagnetic state as the temperature decreases (T_c = 170 K). The second sample, Pr_0.70Ca_0.25Sr_0.05MnO₃, that exhibits an extremely high R₀/R_H ratio (2.5 × 10⁵ at 88 K), shows a transition from the paramagnetic state to an antiferromagnetic state and finally to a canted ferromagnetic state. The presence of an intermediate AF state explains the M(T) curves and the exceptional high magnetoresistive effect. The determination of the nuclear structure of these oxides confirms their ‘O₃’ oxygen stoichiometry and evidences a contraction of the lattice parameters at the ferromagnetic transition. The evolution of the MnO distances shows a decrease of the Jahn-Teller distortion at the magnetic transition.     

Raman phonon spectra and lattice dynamics of 9,10-dinitroanthracene under pressure

Abstract

Raman phonon spectra of 9, 10-dinitroanthracene have been recorded in the pressure range 0-6GPa. No phase transition is detected up to the maximum pressure studied. Quasi Harmonic Lattice Dynamics calculations, based on an atom-atom potential previously modeled on homologous 9,10-disubstituted anthracenes, have been performed. The optimized potential was used to calculate the equilibrium geometry and the lattice phonon frequencies as a function of pressure. The calculated structure at ambient conditions closely resembles the experimental one. The calculated phonon frequencies show a good agreement with the experimental values at all pressures measured.     

Heat capacity of La1−x SrxMnO3 single crystals in different magnetic states

The heat capacity of three single-crystal samples of La_1?x Sr_xMnO₃ (x=0, 0.2, and 0.3) is measured in the temperature range 4–400 K. It is found that the heat capacity undergoes abrupt changes due to the transitions from the antiferromagnetic phase to the paramagnetic phase (x=0) and from the ferromagnetic phase to the paramagnetic phase (x=0.2 and 0.3). The phonon contribution to the heat capacity and the Debye characteristic temperatures for the La_0.7Sr_0.3MnO₃ sample are determined over a wide range of temperatures. The electronic density of states at the Fermi level is evaluated. It is demonstrated that an increase in the strontium concentration x brings about an increase in the electronic density of states at the Fermi level. The contributions of spin waves to the heat capacity and the entropy are estimated under the assumption that the phonon spectrum remains unchanged upon doping with Sr.