Evolution of charge ordering in manganites

Charge ordering phenomena in the manganites Ca_1-xSm_xMnO₃ have been studied for , using electron diffraction and lattice imaging, completed by magnetic and transport measurements. Three domains can be distinguished, depending on the nature of the structural transitions with temperature. For , the structural transition from a pseudo-tetragonal to a monoclinic form, with decreasing temperature, coincides with the competition between ferromagnetism and antiferromagnetism that is characterized by the temperature T_peak on the M ( T ) curves; short-range charge ordering is observed for manganites. For the second domain, , a structural transition from an orthorhombic to a long-range charge ordered state is clearly observed with decreasing temperature. The corresponding temperature T_CO coincides with the temperature T_peak deduced from magnetic measurements. This long range charge ordering, which appears along a, is either commensurate or incommensurate depending on the x value, with a modulation vector, q being close to x. These modulated superstructures correspond to a stacking of single Mn³⁺ stripes with multiple Mn⁴⁺ stripes along a, either in a commensurate or in an incommensurate manner. The third domain , is characterized by a transition to a charge ordered state with commensurate superstructure at low temperature. The latter can be described as a “partially” charge ordered state in which single “Mn³⁺” stripes alternate with mixed “Mn³⁺/Mn⁴⁺” stripes. Received 17 June 1998     

Synchrotron x-ray-diffraction study of α-cristobalite at high pressure and high temperature

Abstract

Energy-dispersive x-ray diffraction using synchrotron radiation was carried out on α-cristobalite to 3 GPa and 350°C in a cubic anvil press. A cascading structural phase transition occurred beyond 0.61 GPa at room temperature. The transition was accompanied by a splitting of most of the a-cristobalite reflections: the (111) reflection at 0.61 GPa through the (211) reflections at 2.13 GPa, with many other lines between. The pressure of this transition decreased with increasing temperature.     

Pressure dependence of crystal structure and molecular packing in anthracene

Anthracene molecular crystal has been investigated up to a pressure of 10.5 GPa at room temperature using variable shape variable size Monte Carlo simulations in an isothermal–isobaric ensemble. We have reported various structural quantities, such as cell parameters and unit cell volume, as a function of pressure and compared them with the experimental results [J. Chem. Phys. 119, 1078 (2003)]. The pressure dependence of angles θ, δ and χ which describe the relative packing of molecules in the crystal has been calculated. We report that anthracene molecular crystal does not exhibit any first order phase transition up to a pressure of 10.5 GPa which is consistent with the experimental observations by Oehzelt et al. [Phys. Rev. B 66, 174104 (2002)]. The calculated equation of state (EOS) has been fitted to a Murnaghan-type EOS with good agreement. The calculated bulk modulus and the pressure derivative of bulk modulus are 8.2 GPa and 8.9 respectively which are in agreement with the experimentally calculated values.     

Study of the ferrodistorsive orbital ordering in NaNiO2 by neutron diffraction and submillimeter wave ESR

NaNiO₂ has been studied by neutron-powder diffraction, magnetic susceptibility and submillimeter wave ESR. The monoclinic structure at room temperature is characterised by a ferrodistorsive orbital ordering due to the Jahn-Teller (JT) effect of the Ni³⁺ ions in the low spin state. NaNiO₂ undergoes a structural transition at around 480 K, above which the orbital ordering disappears. The high temperature phase is rhombohedral with the layered -NaFeO₂ structure ( space group). The magnetic susceptibility exhibits hysteresis and we observe a change of the Curie-Weiss law parameters above the JT transition. The anisotropy of the g-factor at 200 K can be attributed to the JT effect which favours the orbital occupation. Finally, the interplay between the magnetic and structural properties of NaNiO₂ and Li_1-xNi_1+xO₂ is discussed. Received 29 May 2000     

The magnetostriction of Invar alloys

The principles of the theory of a phase transition into a magnetically ordered state are formulated for Invar alloys and other similar inhomogeneous ferromagnets, for which the concept of a local Curie temperature distribution corresponding to the experimentally observed broadened temperature interval of the transition into the ferromagnetic state has existed for 10 years. A method is proposed for obtaining information about the local temperature distribution from experimental data on the change in the properties of magnets in response to a change in temperature. For iron-nickel-chromium alloys it is shown how to obtain the temperature dependence of the magnetostrictional susceptibility of the paraprocess from data on the magnetic contribution to the thermal expansion coefficient. This confirms the important role of the local Curie temperature distribution, and it also indicates a need for new analysis of experimental data on temperature-broadened magnetic ordering phase transitions. Zh. éksp. Teor. Fiz. 113, 213–227 (January 1998)     

Metastable phases in vapour-quenched Al78Cu22 film

The structure and structural changes of an Al₇₈Cu₂₂ (at%) alloy film produced by coevaporation onto a cooled substrate have been investigated with transmission electron microscopy. A series of metastable phase transitions were observed during the crystallization from the as-deposited amorphous phase to the final equilibrium state. The deposit structure at room temperature consists of a mixture of fine grained α' crystallites (fcc, α = 4.81 Å) with an amorphous phase, and some welldefined crystals with an fcc lattice (a = 7.18 Å, namely α₁). The subsequent annealing led to the grown crystals transforming to an ordered α′ phase. It is argued that the development of such a transition is the result of a gradual atomic rearrangement – first topologically then a chemically predominant disorder-order transition.     

Phase diagram and equations of state of BaSO4

Abstract

The phase diagram and equations of state of BaSO₄, were determined up to 29 GPa and 1000 K in a resistance-heating type diamond anvil cell. At room temperature, barite is the stable form of BaSO₄ which undergoes a reversible phase transition at 10 GPa. The high-pressure form is tentatively determined to be triclinic. At high temperature, a similar phase transition takes place in BaSO₄, but at a pressure higher than that at room temperature. Our results indicate that the phase boundary of the two polymorphs in BasO₄ has a positive slope (dT/dP) of 90 K/GPa. The equations of state for both barite and its high-pressure phase are reported.     

Thermal expansion and spontaneous strain of KMnF3 near the 186 K-structural phase transition

Abstract

By means of high-angle double-crystal X-ray diffractometry (HADOX), the thermal expansivity of KMnF₃ has been determined. The linear thermal expansion coefficient along each crystallographic axis exhibits a divergent anomaly at the structural phase transition at 186 K. The critical exponents of these coefficients are determined: in the cubic phase α = 0.21 ± 3, and in the tetragonal phase α′ = 0.19 ± 3 for the a axis and α″ = 0.35 ± 3 for the c axis.

In addition, the critical exponent of the spontaneous strain, c/a ? 1, is determined to be 0.4248 ± 8, which is smaller than that of the order parameter 2β = 0.5714 ± 12. These values are reasonable if the transition occurs in the vicinity of a tricritical point.     

First-principles study of structural,elastic, electronic and optical properties of RDX under pressure

ABSTRACT

The influences of pressure on structural, elastic, electronic and optical properties of α-RDX under pressure from 0 to 40?GPa have been investigated by performing first-principles calculations. The obtained structural parameters based on the GGA-PBE+G calculations are consistent with previous experimental values. The results of B/G, C₁₂-C₄₄ and Poisson's ratio show that α-RDX has changed to ductility under pressure between 0 and 5?GPa. The obvious rotation of NO₂ group in the equatorial position appears, especially in the range of pressure from 10 to 15?GPa, which influences the elastic and mechanical properties of α-RDX. Moreover, we find that the electrons of α-RDX become more active under higher pressure by comparing the curves of DOS under different pressure. Furthermore, the anisotropy of optical properties under different pressures has been shown.     

Temperature dependence of the giant magnetostriction of submicrocrystalline dysprosium

The temperature dependence of the magnetostriction of Dy was measured in various structural states. A submicrocrystalline state was created by intense plastic deformation on Bridgman anvils. Intermediate-and large-grain states were obtained by annealing samples in a vacuum at 573 and 873 K respectively. In the large-grain state, plots of the magnetostriction versus temperature exhibit a kink at around 85 K, which is evidence of a magnetic phase transition from ferromagnetism to helical antiferromagnetism. In the submicrocrystalline state these curves have no kinks and decrease smoothly to zero at high temperatures. This is interpreted as the absence of helical antiferromagnetic order in the sample. Fiz. Tverd. Tela (St. Petersburg) 41, 1665–1667 (September 1999)     

Behavior of the atomic and magnetic structure of La0.35Pr0.35Ca0.30MnO3 at a metal-insulator phase transition

The evolution of the structural and magnetic properties of the CMR (colossal-magnetoresistance) compound La_0.35Pr_0.35Ca_0.30MnO₃ as the temperature changes from 10 to 293 K is investigated by means of neutron diffraction. It is shown that the changes in the transport and magnetic properties are directly related with the rearrangement of the atomic structure. A phase transition to the metallic state occurs together with simultaneous ferromagnetic ordering of the manganese moments and is accompanied by a jump in volume. The static distortions of the oxygen octahedra which are observed to occur prior to the magnetic phase transition and which are practically absent at room temperature and in the FM phase attest to the orbital ordering of oxygen atoms on the bonds, with freezing-in of the Jahn-Teller modes. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 9, 672–677 (10 May 1998)     

Influence of disorder in crystal structure on ferroelectric phase transitions

A new model of ferroelectric phase transitions in disordered crystals is developed. The model takes into account the nonequivalence of the structural environment of identical ions, which alters the balance of forces governing ferroelectric structural instability. In contrast with its predecessors, the new model can be used for qualitative and, in many cases, quantitative predictions of the temperature range of the diffuse ferroelectric phase transition and the value of the disorder-induced shift of the average transition temperature as a function of the degree of disorder and chemical composition. This conclusion is confirmed by a comparison of the theoretical results with an abundance of known experimental facts. Zh. éksp. Teor. Fiz. 111, 1817–1832 (May 1997)     

First-principles study of the high pressure phase transition and lattice dynamics of cerium

We present a first-principles study of the phase transition and lattice dynamics of Ce within the framework of the density functional theory using the GGA+U method. Our calculated results denote that under pressure the transition path is α-Ce (fcc)→α″-Ce (monoclinic, with two atoms per unit cell)→bct-Ce (body centered tetragonal), and the transition pressures are located at 5.36 and 14.37 GPa, respectively. The equation of state in a wide range of pressure is consistent with the experimental data. During the γ-α phase transition, the magnetic moment disappears gradually, which is mainly due to the strong interaction between the 4f and 5d electrons. By calculating the free energies from phonon dispersions including electronic contribution, the obtained γ-α transition temperature at zero pressure is 148 K. From the Blackman diagram of dimensionless elastic constant ratios, we can find that both γ- and α-Ce show negative Cauchy pressure—C₄₄>C₁₂.     

Mass spectrometric investigation of low-temperature diffusion and solubility of helium in lead fluoride crystals

Thermal desorption of helium from presaturated crystals was used for mass spectrometric investigations of the diffusion and solubility of helium in lead fluoride crystals in the temperature range 606–714K which precedes the transition of the crystal to the superionic state. The experimental apparatus and measurement method are described and mechanisms for the diffusion and solubility of helium in PbF₂ are discussed. Zh. Tekh. Fiz. 68, 85–89 (December 1998)     

Kinetics of structural relaxation and regularities of plastic flow of metallic glasses

On the basis of a calculation of the structural relaxation rate and an experimental acoustical-emission determination of the temperature of the transition from localized to uniform flow it is argued that the type of plastic deformation of metallic glasses is uniquely determined by the kinetic structure of the relaxation. In the case of a kinetically hindered structural relaxation, which is characteristic for tests of initial samples at temperatures T<380–420 K, a localized dislocational deformation is realized. At higher temperatures, “memory” of the thermal prehistory of the samples is lost (aging at room temperature), the structural relaxation rate grows abruptly and plastic flow becomes uniform viscoplastic flow. Fiz. Tverd. Tela (St. Petersburg) 41, 2167–2173 (December 1999)     

Infrared spectroscopy and ultrasonic velocimetry as a tool for probing conformational flexibility of proteins

Abstract

Because of the crucial importance of structural fluctuations for function and stability of proteins, there is a strong interest for the relationships between structural fluctuations, the parameters of protein denaturation and the kinetics of H/D-exchange. Structural fluctuations can be described by volume and entropy fluctuations and these quantities are accessible via the isothermal compressibility, the thermal expansion and the isobaric heat capacity.

Our aim is to present the principal problem concerning the experimental procedures to answer those questions using lysozyme and α-lactalbumin. Whereas the transition parameters and the kinetics of the H/D-exchange were obtained using FTIR spectroscopy, the adiabatic compressibility was obtained by a combination of ultrasonic velocimetry and densitometry. It could be shown that the stability of the investigated proteins is correlated with reduced volume fluctuations. The expected direct correlation between H/D exchange rates and structural fluctuations could not be seen and it is assumed that the interactions are more complex than from the intuitive point of view.     

The magnesium doping effect of the vanadate spinel MnV2O4

We investigate the structural, transport, and magnetic properties of Mn_1−xMg_xV₂O₄(0≤x≤0.8) to study the role of the A-site magnetism in vanadate spinels. With increasing Mg²⁺ concentration, the lattice parameters shrink and the hopping energy for electrons increases, whereas both the magnetic transition temperature and the structural transition temperature decrease gradually. The two temperatures become closer and eventually equal to each other at x=0.2. For x>0.2 the first order transition disappears and the magnetic ground state switches from a long range ordered ferrimagnetic state to a glassy state. The transition temperature of the glassy state continues to decrease with further increase of Mg content, which is attributed to the dilution in the magnetism on A sites.     

Argentite-Acanthite Transformation in Silver Sulfide as a Disorder-Order Transition

An alternative model has been proposed for the phase transition from cubic argentite ß-Ag₂S to monoclinic acanthite α-Ag₂S in silver sulfide as a disorder–order transition. It has been shown that, as the temperature decreases below the transition temperature T_trans, S atoms equiprobably occupying the sites of the body centered cubic (bcc) nonmetal sublattice of argentite are concentrated at four sites of the monoclinic nonmetal sublattice, whereas the other sites remain vacant. A disorder-order transition channel including three superstructure vectors of k₉ and k₄ stars has been determined. The distribution function of sulfur atoms in monoclinic acanthite α-Ag₂S has been calculated. It has been shown that displacements of sulfur atoms distort the bcc nonmetal sublattice of argentite, forming a monoclinic lattice, where silver atoms are spaced by quite large distances and occupy their crystallographic positions with a probability of 1. The region of allowed values of the long-range order parameters η₉ and η₄ for the model monoclinic ordered phase α-Ag₂S has been determined.

     

传压介质对晶格振动和相变压力的影响——α-Bi2O3的高压拉曼光谱研究

 本文分别使用4∶1的甲醇-乙醇混合溶液和固态氩做传压介质测量α-Bi₂O₃的高压拉曼光谱。实验结果表明，传压介质对样品的谱线频移速率及相变压力有明显的影响。通过对拉曼光谱的分析认定，α-Bi₂O₃在高压下可能经历了一次结构相变，在准静水压和非静水压条件下的相变压力分别为23.1 GPa和20.4 GPa。     

Elastic,electronic and thermal properties of topological insulator SmB6: first-principles calculations

Abstract

The pressure dependence of the structural, elastic, electronic and thermal properties of Kondo insulator SmB₆ have been systematically studied by density functional theory combined with the quasi-harmonic Debye model. The calculated structure at zero pressure is in good agreement with the available experimental results at low temperature. The obtained elastic constants, bulk modulus and shear modulus indicate that SmB₆ is mechanically stable and behaves in a brittle manner under the applied pressure 0–20 GPa, consistent with available experimental data. In addition, the elastic-relevant properties, Young’s modulus and the Poisson ratio manifest that increasing pressure results in an enhancement in the stiffness of the compound. It is found that unlike temperature, pressure has little effect on the heat capacity of SmB_6. What more important is that we observed an insulator to metal phase transition at about 5.5 GPa through the disappearance of the band gap, well consistent with the experimental data. This transition has little effect on the physical properties of SmB₆.