Molecular dynamics simulation of phase transition in AgNO3

Structural phase transition in AgNO₃ at high temperature is simulated by molecular dynamics. The simulations are based on the potentials calculated from the Gordon-Kim modified electron-gas formalism extended to molecular ionic crystals. AgNO₃ transforms into rhombohedral structure at high temperature and the phase transition is associated with the rotations of the NO₃ ions and displacements of the NO₃ and Ag ions.     

High pressure phase transition and elastic properties of thorium chalcogenides

The structural and elastic properties of thorium chalcogenides at high pressure, have been investigated using a suitable inter-ionic potential. The calculated equation of state, phase transition pressures for B1-B2 transition and bulk moduli for ThX (X=S,Se,Te) compounds agree well with the experimental results. ThTe, which crystallizes in the CsCl structure, does not show any structural transition up to 48 GPa. The present analysis does not show any anomalous features in elastic properties arising from ‘f’ electrons.     

Synthesis and structure refinement of layered perovskites Ba5−xLaxNb4−xTixO15 (x=0, 1, 2, 3 and 4) solid solutions

Ba_5−xLa_xNb_4−xTi_xO₁₅ solid solutions were prepared by solid state reaction method. Structural analysis for the stoichiometric phases was performed for x=0, 1, 2 and 3 by Rietveld analysis of neutron powder diffraction data. The x=0, 1 and 2 members could be refined in the space group P-3m1 (stacking sequence chhcc, polytypoid 5 H). There is a decrease in cell volume as x increases. La³⁺ occupies preferentially the A2 site (Wyckoff site 2d) and Ti⁴⁺ the B2 site (Wyckoff site 2c). As x increases there is an increase of the global instability index (GII) (which is a measure of the extent to which the BVS rule is violated over the whole structure) indicating the presence of intrinsic strains large enough to cause instability at room temperature. This strain is responsible for a structural change for the member with x=3, which could be refined in the space group P-3c1 (stacking sequence (chhcc)₂, polytypoid 2×5H=10H). This change in space group is associated with a cooperative rotation of (Nb/Ti)O₆ octahedra around the c-axis, necessary to accommodate the smaller La³⁺ ion in the cuboctahedral cavity.     

Local magnetization study of the first-order superconducting transition in CeCoIn5

We report local magnetization measurements on the heavy fermion superconductor CeCoIn₅ using a micro-Hall probe. Below a critical point T₀ (), the local magnetization shows a clear jump at the superconducting transition temperatures for both H∥a and H∥c, indicating that the phase transition at the upper critical field H_c2 becomes a first-order phase transition. In addition, we observed an undershoot behavior of magnetization jump above (H∥c), which suggests a rapid change of textured superconducting structure with vortices and the nodal planes expected in the Fulde-Ferrell-Larkin-Ovchinnikov state.     

Enhanced ferromagnetism in Mn-doped TiO2 films during the structural phase transition

The crystal structures and magnetic properties of Ti_0.9747Mn_0.0253O₂ films prepared by sol–gel dip coating have been investigated. Room temperature ferromagnetism was observed both in the films of pure anatase phase and of mixed anatase and rutile phases. For the first time, enhancement of the ferromagnetism was revealed as the phase transition from anatase to rutile occurs: from 0.7±0.01μ_B/Mn to 1.1±0.05μ_B/Mn. The possible mechanism for the observed magnetism enhancement is discussed.     

Low temperature structural phase transition in hafnium and zirconium tetrafluoride trihydrates

From time-differential perturbed angular correlation (TDPAC) measurements, the monoclinic and triclinic crystal structures in hafnium and zirconium tetrafluoride trihydrates are found to be present simultaneously in both the compounds. From previous TDPAC and XRD investigations, a monoclinic crystal structure for HfF₄·3H₂O but, for its analogues zirconium compound, a triclinic structure was reported. Contrary to earlier reports, the triclinic fraction in HfF₄·3H₂O is found to be maximum (80%) at room temperature. In fact, the triclinic crystal structure of HfF₄·3H₂O is reported here which was not known prior to this report. In ZrF₄·3H₂O, a strong signal (80–90%) for the triclinic structure is found at room temperature while the monoclinic fraction appears as a weak signal (10–15%). Structural phase transitions in these trihydrate compounds have been observed in the temperature range 298–333 K.     

Heat capacity and magnetic phase transitions of rare-earth orthoferrite HoFeO3

Heat capacity of two rare-earth orthoferrites HoFeO₃ and LuFeO₃ were measured between 1.8 and 200 K. A distinctly large and two small heat capacity anomalies were detected for HoFeO₃ under zero magnetic field around 3.3, 53 and 58 K, respectively. The low-temperature anomaly with a peak at 3.3 K is due to the ordering of Ho³⁺ ions and the estimated magnetic entropy for this transition was favorably compared with the expected (R ln 2). Application of magnetic field significantly affects the positions and the magnitudes of the anomaly at 3.3 K. Energies of low-lying levels of the lowest J-term of Ho³⁺ ion were roughly estimated through analysis of the Schottky heat capacity.     

Intermediate-temperature polymorphic phase transition in KH2PO4: A synchrotron X-ray diffraction study

We have used synchrotron X-ray diffraction to investigate the structural and chemical changes undergone by polycrystalline KH₂PO₄ (KDP) upon heating within the 30-250 °C temperature interval. Our data show evidence of a polymorphic transition at T∼190 °C from the room-temperature tetragonal KDP phase to a new intermediate-temperature monoclinic KDP modification (spacegroup P2₁/m and lattice parameters a=7.590, b=6.209, c=4.530 Å, and β=107.36°). The monoclinic RDP polymorph remains stable upon further heating to 235 °C, and is isomorphic to its RbH₂PO₄ and CsH₂PO₄ counterparts.     

Room temperature stable structures and phase transition of Na2Al2B2O7

By Rietveld refinement of the X-ray diffraction (XRD) data of powdered Na₂Al₂B₂O₇ samples aged for over 3 months, we found that Na₂Al₂B₂O₇ at room temperature is a mixture of two phases with space group and P6₃/m, respectively. The structures of the two phases can be refined with identical cell parameters of a=4.80760(11) Å, c=15.2684(5) Å and are composed by [Al₂B₂O₇]²⁻_∝ double layers stacking alternatively with Na⁺ ions along the c-direction, but differ at in-plane bond orientations of the BO₃/AlO₄ groups within the double layers: in P6₃/m phase B-O₁/Al-O₁ bonds of the two layers are perfectly aligned, whereas in phase they are twisted by 46.4/41.6° around c-axis against each other. It is also found that a freshly prepared sample contains only the phase, but part of the phase will transfer to P6₃/m phase slowly at room temperature and the transition can be reversed by heating the aged sample above 220 °C.     

In situ high-pressure X-ray diffraction study of densification of a molecular chalcogenide glass

Structural mechanisms of densification of a molecular chalcogenide glass of composition Ge_2.5As_51.25S_46.25 have been studied in situ at pressures ranging from 1 atm to 11 GPa at ambient temperature as well as ex situ on a sample quenched from 12 GPa and ambient temperature using high-energy X-ray diffraction. The X-ray structure factors display a reduction in height of the first sharp diffraction peak and a growth of the principal diffraction peak with a concomitant shift to higher Q-values with increasing pressure. At low pressures of at least up to 5 GPa the densification of the structure primarily involves an increase in the packing of the As₄S₃ molecules. At higher pressures the As₄S₃ molecules break up and reconnect to form a high-density network with increased extended-range ordering at the highest pressure of 11 GPa indicating a structural transition. This high-density network structure relaxes only slightly on decompression indicating that the pressure-induced structural changes are quenchable.     

Phase transition behavior and proton conduction mechanism in cesium hydrogen sulfate/silica composite

Proton conduction and crystal structure in CsHSO₄/SiO₂ composite composed of polycrystalline CsHSO₄ and mesoporous silica particles were investigated based on conductivity measurement and characterizations using Raman spectroscopy, XRD, and differential thermal analysis. The conductivity of pure CsHSO₄ abruptly changes at around 414 K (superprotonic phase transition), being accompanied with the structural transformation from a monoclinic phase to a tetragonal phase, while the conductivity of CsHSO₄/SiO₂ composite is significantly larger by over three orders of magnitude than that of pure CsHSO₄ below the critical temperature of the superprotonic phase transition (353-414 K). Raman spectroscopy and XRD indicate that this remarkable conductivity-enhancement in the composite is not due to the stabilization of the tetragonal phase (superprotonic phase) below its critical temperature. The line-broadening of the internal modes in the Raman spectra suggests that the rapid reorientational motion of the HSO₄⁻ ion, which leads to superprotonic conduction, is induced in the composite even below the critical temperature. The reorientational motion of the HSO₄⁻ ion below the critical temperature will occur at the interfacial phase which is structurally disordered and forms between CsHSO₄ and SiO₂ in the mesopores and/or on the surfaces of silica particles. Proton transfer will be accelerated via the interfacial conduction-pathway in the composite.     

Tuning hydrogen storage properties and reactivity: Investigation of the LiBH4-NaAlH4 system

Tuning the hydrogen storage properties of complex metal hydrides is of vast interest. Here, we investigate the hydrogen release and uptake pathways for a reactive hydride composite, LiBH₄−NaAlH₄ utilizing in situ synchrotron radiation powder X-ray diffraction experiments. Sodium alanate transforms to sodium borohydride via a metathesis reaction during ball milling or by heating at T∼95 °C. NaBH₄ decomposes at ∼340 °C in dynamic vacuum, apparently directly to solid amorphous boron and hydrogen and sodium gas and the latter two elements are lost from the sample. Under other conditions, T=400 °C and p(H₂)=∼1 bar, NaBH₄ only partly decomposes to B and NaH. On the other hand, formation of LiAl is facilitated by dynamic vacuum conditions, which gives access to the full hydrogen contents in the LiBH₄−NaAlH₄ system. Formation of AlB₂ is observed (T∼450 °C) and other phases, possibly AlB_x or Al_1−xLi_xB₂, were observed for the more Li-rich samples. This may open new routes to the stabilization of boron in the solid state in the dehydrogenated state, which is a challenging and important issue for hydrogen storage systems based on borohydrides.     

Study of quantum effects on atomic displacements in quartz

The crystal structure of quartz (SiO₂) was analyzed by neutron powder diffraction at several temperatures in the range of 10-250 K. The temperature dependence of the structure parameters was consistent with our previous results obtained using single-crystal X-ray diffraction above room temperature. Atomic displacements are order parameters for displacive structural phase transitions. The temperature evolution of Si atomic displacement in quartz was analyzed by studying the quantum expansion of the Landau potential. The expansion was found to accurately describe the evolution of the atomic displacement over the entire temperature interval. To the best of our knowledge, such a verification of atomic displacement is the first of its kind. A proportional relationship between spontaneous strain and the square of the atomic displacement was observed over the entire temperature interval. The validity of the obtained characteristic temperature for the quantum effect is discussed and compared with the results of previous Raman-scattering studies.     

Brillouin scattering study of phase transitions in LiK0.80(NH4)0.20SO4 mixed crystals

Brillouin spectroscopy was used to study the phase transitions of LiK_0.80(NH₄)_0.20SO₄ mixed crystals in the temperature range 10-300 K. The relevant elastic stiffness coefficients were evaluated at room temperature. The quasi-longitudinal γ₁₆ and the quasi-transverse γ₁₇ mode frequencies were measured in the above temperature range. From their frequency vs. temperature curve, three different phase transitions were determined. Two of the four phases presented by the crystal were found to be ferroelastic. The observed phases are tentatively assigned through a comparison with the phase transitions undergone by LiKSO₄ and LiK_0.96(NH₄)_0.04SO₄ crystals. An anomalous behavior of the Brillouin linewidth near the 260 K phase transition was observed.     

Powder-neutron diffraction studies of geometric isotope and hydrogen-bonding effects in β-CrOOH

Powder-neutron diffraction studies have been done on β-CrOOH and β-CrOOD to confirm whether or not the reported exceptionally large geometric isotope effect is real, and also to study hydrogen-bonding effects in β-CrOOH compared to the prototype CrO₂. The R(O?O) distance in the H-compound at room temperature is confirmed to be 2.472(3) Å, but in the D-compound it is significantly shorter, 2.518(3) Å, than in the earlier work. The resulting magnitude of the geometric isotope effect, 0.046(4) Å, is thus not as exceptionally large as earlier reported, but is still within the maximum range. Structural comparison with CrO₂ clarified the hydrogen-bonding effect in β-CrOOH: the formation of hydrogen bonds brings CrO₆ closer to a regular octahedron.     

Magnetic properties of the ferrimagnetic cobaltite CaBaCo4O7

The magnetic properties of the ferrimagnetic cobaltite CaBaCo₄O₇ are systematically investigated. We find that the susceptibility exhibits a downward deviation below ∼360 K, suggesting the occurrence of short-range magnetic correlations at a temperature well above T_C. The effective moment is determined to be ., which is consistent with that expected for the Co²⁺/Co³⁺ high spin species. Using a criterion given by Banerjee [Phys. Lett. 12 (1964) 16], we demonstrate that the paramagnetic to ferrimagnetic transition in CaBaCo₄O₇ has a first order character.     

Experimental constraints on the phase diagram of elemental zirconium

The phase diagram of zirconium metal has been studied using synchrotron X-ray diffraction and time-of-flight neutron scattering at temperatures and pressures up to 1273 K and 17 GPa. The equilibrium phase boundary of the α-ω transition has a dT/dP slope of 473 K/GPa, and the extrapolated transition pressure at ambient temperature is located at 3.4 GPa. For the ω-β transition, the phase boundary has a negative dT/dP slope of 15.5 K/GPa between 6.4 and 15.3 GPa, which is substantially smaller than a previously reported value of −39±5 K/GPa in the pressure range of 32-35 GPa. This difference indicates a significant curvature of the phase boundary between 15.3 and 35 GPa. The α-ω-β triple point was estimated to be at 4.9 GPa and 953 K, which is comparable to previous results obtained from a differential thermal analysis. Except for the three known crystalline forms, the β phase of zirconium metal was found to possess an extraordinary glass forming ability at pressures between 6.4 and 8.6 GPa. This transformation leads to a limited stability field for the β phase in the pressure range of 6-16 GPa and to complications of high-temperature portion of phase diagram for zirconium metal.     

Nature of the quantum spin correlations through the superconducting-normal phase transition in electron-doped superconducting Pr0.88LaCe0.12CuO4

We use neutron scattering and specific heat measurements to relate the response of the spin fluctuations and static antiferromagnetic (AF) order to the superconductivity in the electron-doped high-transition-temperature superconductor, Pr_.88LaCe_.12CuO_4−δ (PLCCO) (T_c=24 K), as the system is tuned via a magnetic field applied beyond the upper critical field (H_c2) and driven into the normal state. The strength of the collective magnetic excitation commonly termed “resonance” decreases smoothly with increasing field and vanishes in the normal state, paralleling the behavior of the superconducting condensation energy. The suppression of superconductivity is accompanied by a smooth reduction in the very low energy spin fluctuations, and the concomitant emergence of static AF order. Our results suggest an intimate connection between the resonance and the superconducting condensation energy.