Ice XV: A New Thermodynamically Stable Phase of Ice

A new phase of ice, named ice XV, has been identified and its structure determined by neutron diffraction. Ice XV is the hydrogen-ordered counterpart of ice VI and is thermodynamically stable at temperatures below similar to 130 K in the 0.8 to 1.5 GPa pressure range. The regions of stability in the medium pressure range of the phase diagram have thus been finally mapped, with only hydrogen-ordered phases stable at 0 K. The ordered ice XV structure is antiferroelectric (P1), in clear disagreement with recent theoretical calculations predicting ferroelectric ordering (Cc)

Temperature and field dependence of the phase separation, structure, and magnetic ordering in La1−x_{1-x}Cax_xMnO3_3, (x=0.47x=0.47, 0.50, and 0.53)

Neutron powder diffraction measurements, combined with magnetization and resistivity data, have been carried out in the doped perovskite La$_{1-x}$Ca$_x$MnO$_3$ ($x=0.47$, 0.50, and 0.53) to elucidate the structural, magnetic, and electronic properties of the system around the composition corresponding to an equal number of Mn3+ and Mn4+. At room temperature all three samples are paramagnetic and single phase, with crystallographic symmetry Pnma. The samples then all become ferromagnetic (FM) at $T_C\approx 265$ K. At $\sim 230$ K, however, a second distinct crystallographic phase (denoted A-II) begins to form. Initially the intrinsic widths of the peaks are quite large, but they narrow as the temperature decreases and the phase fraction increases, indicating microscopic coexistence. The fraction of the sample that exhibits the A-II phase increases with decreasing temperature and also increases with increasing Ca doping, but the transition never goes to completion to the lowest temperatures measured (5 K) and the two phases therefore coexist in this temperature-composition regime. Phase A-II orders antiferromagnetically (AFM) below a N\'{e}el temperature $T_N \approx 160$ K, with the CE-type magnetic structure. Resistivity measurements show that this phase is a conductor, while the CE phase is insulating. Application of magnetic fields up to 9 T progressively inhibits the formation of the A-II phase, but this suppression is path dependent, being much stronger for example if the sample is field-cooled compared to zero-field cooling and then applying the field. The H-T phase diagram obtained from the diffraction measurements is in good agreement with the results of magnetization and resistivity.Comment: 12 pages, 3 tables, 11 figure

Optical study of MgTi2_2O4_4: Evidence for an orbital-Peierls state

Dimension reduction due to the orbital ordering has recently been proposed to explain the exotic charge, magnetic and structural transitions in some three-dimensional (3D) transitional metal oxides. We present optical measurement on a spinel compound MgTi$_2$O$_4$ which undergoes a sharp metal-insulator transition at 240 K, and show that the spectral change across the transition can be well understood from the proposed picture of 1D Peierls transition driven by the ordering of $d_{yz}$ and $d_{zx}$ orbitals. We further elaborate that the orbital-driven instability picture applies also very well to the optical data of another spinel CuIr$_2$S$_4$ reported earlier.Comment: 5 pages, 6 figures, to be published in Phys. Rev.

Atomic-scale images of charge ordering in a mixed-valence manganite

Transition-metal perovskite oxides exhibit a wide range of extraordinary but imperfectly understood phenomena. Charge, spin, orbital, and lattice degrees of freedom all undergo order-disorder transitions in regimes not far from where the best-known of these phenomena, namely high-temperature superconductivity of the copper oxides, and the 'colossal' magnetoresistance of the manganese oxides, occur. Mostly diffraction techniques, sensitive either to the spin or the ionic core, have been used to measure the order. Unfortunately, because they are only weakly sensitive to valence electrons and yield superposition of signals from distinct mesoscopic phases, they cannot directly image mesoscopic phase coexistence and charge ordering, two key features of the manganites. Here we describe the first experiment to image charge ordering and phase separation in real space with atomic-scale resolution in a transition metal oxide. Our scanning tunneling microscopy (STM) data show that charge order is correlated with structural order, as well as with whether the material is locally metallic or insulating, thus giving an atomic-scale basis for descriptions of the manganites as mixtures of electronically and structurally distinct phases.Comment: 8 pages, 4 figures, 19 reference

Nature of ege_g Electron Order in La1−x_{1-x}Sr1+x_{1+x}MnO4_4

Synchrotron x-ray scattering measurements of the low-temperature structure of the single-layer manganese oxide La$_{1-x}$Sr$_{1+x}$MnO$_4$, over the doping range $0.33 \le x \le 0.67$, indicate the existence of three distinct regions: a disordered phase ($x < 0.4$), a charge-ordered phase ($x \ge 0.5$), and a mixed phase ($0.4 \le x 0.5$, the modulation vector associated with the charge order is incommensurate with the lattice and depends linearly on the concentration of $e_g$ electrons. The primary superlattice reflections are strongly suppressed along the modulation direction and the higher harmonics are weak, implying the existence of a largely transverse and nearly sinusoidal structural distortion, consistent with a charge density wave of the $e_g$ electrons.Comment: 4 pages, 4 figure

Cooling rate dependence of the antiferromagnetic domain structure of a single crystalline charge ordered manganite

The low temperature phase of single crystals of Nd$_{0.5}$Ca$_{0.5}$MnO$_3$ and Gd$_{0.5}$Ca$_{0.5}$MnO$_3$ manganites is investigated by squid magnetometry. Nd$_{0.5}$Ca$_{0.5}$MnO$_3$ undergoes a charge-ordering transition at $T_{CO}$=245K, and a long range CE-type antiferromagnetic state is established at $T_N$=145K. The dc-magnetization shows a cooling rate dependence below $T_N$, associated with a weak spontaneous moment. The associated excess magnetization is related to uncompensated spins in the CE-type antiferromagnetic structure, and to the presence in this state of fully orbital ordered regions separated by orbital domain walls. The observed cooling rate dependence is interpreted to be a consequence of the rearrangement of the orbital domain state induced by the large structural changes occurring upon cooling.Comment: REVTeX4; 7 pages, 4 figures. Revised 2001/12/0

Spin moment over 10-300 K and delocalization of magnetic electrons above the Verwey transition in magnetite

In order to probe the magnetic ground state, we have carried out temperature dependent magnetic Compton scattering experiments on an oriented single crystal of magnetite (Fe$_3$O$_4$), together with the corresponding first-principles band theory computations to gain insight into the measurements. An accurate value of the magnetic moment $\mu_S$ associated with unpaired spins is obtained directly over the temperature range of 10-300K. $\mu_S$ is found to be non-integral and to display an anomalous behavior with the direction of the external magnetic field near the Verwey transition. These results reveal how the magnetic properties enter the Verwey energy scale via spin-orbit coupling and the geometrical frustration of the spinel structure, even though the Curie temperature of magnetite is in excess of 800 K. The anisotropy of the magnetic Compton profiles increases through the Verwey temperature $T_v$ and indicates that magnetic electrons in the ground state of magnetite become delocalized on Fe B-sites above $T_v$.Comment: 5 pages, 5 figures, to appear in Journal of Physics and Chemistry of Solid

Neutron scattering study of the effects of dopant disorder on the superconductivity and magnetic order in stage-4 La_2CuO_{4+y}

We report neutron scattering measurements of the structure and magnetism of stage-4 La_2CuO_{4+y} with T_c ~42 K. Our diffraction results on a single crystal sample demonstrate that the excess oxygen dopants form a three-dimensional ordered superlattice within the interstitial regions of the crystal. The oxygen superlattice becomes disordered above T ~ 330 K, and a fast rate of cooling can freeze-in the disordered-oxygen state. Hence, by controlling the cooling rate, the degree of dopant disorder in our La_2CuO_{4+y} crystal can be varied. We find that a higher degree of quenched disorder reduces T_c by ~ 5 K relative to the ordered-oxygen state. At the same time, the quenched disorder enhances the spin density wave order in a manner analogous to the effects of an applied magnetic field.Comment: 4 figures included in text; submitted to PR

Trimer Formation and Metal-Insulator Transition in Orbital Degenerate Systems on a Triangular Lattice

As a prototypical self-organization in the system with orbital degeneracy, we theoretically investigate trimer formation on a triangular lattice, as observed in LiVO2. From the analysis of an effective spin-orbital coupled model in the strong correlation limit, we show that the previously-proposed orbital-ordered trimer state is not the lowest-energy state for a finite Hund's-rule coupling. Instead, exploring the ground state in a wide range of parameters for a multiorbital Hubbard model, we find an instability toward a different orbital-ordered trimer state in the intermediately correlated regime in the presence of trigonal crystal field. The trimer phase appears in the competing region among a paramagnetic metal, band insulator, and Mott insulator. The underlying mechanism is nesting instability of the Fermi surface by a synergetic effect of Coulomb interactions and trigonal-field splitting. The results are compared with experiments in triangularlattice compounds, LiVX2 (X=O, S, Se) and NaVO2.Comment: 4 pages, 4 figures, accepted for publication in J. Phys. Soc. Jp

Structural response to O*-O' and magnetic transitions in orthorhombic perovskites

We present a temperature dependent single crystal x-ray diffraction study of twinned orthorhombic perovskites La1-xCaxMnO3, for x=0.16 and x=0.25. These data show the evolution of the crystal structure from the ferromagnetic insulating state to the ferromagnetic metallic state. The data are modelled in space group Pnma with twin relations based on a distribution of the b axis over three perpendicular cubic axes. The twin model allows full structure determination in the presence of up to six twin fractions using the single crystal x-ray diffraction data.Comment: 13 pages, including 13 figures and 2 table