Magnetic ordering in non-centrosymmetric CePdAl3_{3} and CePtAl3_{3}

Owing to the hybridization of cerium's localised 4$f$ electron and conduction band composed of $d$-electrons, cerium based intermetallics exhibit various kinds of magnetic interactions. In crystals, these can result in exotic types of magnetic ordering. In this study, we report a detailed single-crystal neutron diffraction study on CePdAl$_3$ and CePtAl$_3$. We have synthesized a large crystal of CePdAl$_3$, which crystallizes in a non-centrosymmetric, orthorhombic structure with space group $Cmc2_1$, a new, distorted variant of the tetragonal BaNiSn$_3$ structure observed in other Ce$T$Al$_3$ compounds, such as CePtAl$_3$. Low-temperature diffraction measurements showed that CePdAl$_3$ orders in a collinear antiferromagnetic structure below T$_N$=5.3 (1) K, with magnetic moments pointing along the $a$-axis direction and an ordered magnetic moment $\mu$=1.64(3) $\mu_B$/Ce$^{3+}$. Tetragonal CePtAl$_3$ shows a modulated, cycloidal type of ordering with $\vec{k}=(\frac{2}{3}\,0\,0)$, and a transition temperature T$_N$=3.2 K. Symmetry analysis allows two types of ordering, which show modulation of both amplitude and direction of magnetic moments. These results allow to conclude that in Ce$T$Al$_3$ system the orthorhombic distortion ($T$=Pd, Ag) releases some underlying magnetic frustration that results in modulated types of magnetic ordering in tetragonal compounds ($T$=Cu,Au,Pt)

Pressure-induced charge ordering transition in CaMn7O12

We use high-pressure resistivity and single crystal x-ray diffraction at ambient and low temperature to investigate the charge ordering phase transition of CaMn 7 O 12 . We have found that at ambient temperature the Jahn-Teller distortion of the Mn 3 + O 6 octahedra rapidly decreases above 20 GPa, and vanishes at 28 GPa, when two Mn octahedral sites initially occupied by Mn 3 + and Mn 4 + become regular and equivalent as the result of a charge delocalization. Such a change correlates with a two orders of magnitude drop in the resistivity and a symmetry increase from the low-pressure rhombohedral R ¯ 3 phase to the cubic Im ¯ 3 structure, the same as one found at ambient pressure above 440 K. This yields the slope of the charge ordering phase boundary of d T c / d p ? ? 6 K/GPa. This result is further supported by the lack of a structural phase transition up to the maximum measured pressure of 30 GPa when the experiment is performed at 70 K. The satellite reflections of the structural modulation of the multiferroic phase of CaMn 7 O 12 observed at 70 K were found to hold up to 25 GPa with the structure keeping a constant modulation vector k = ( 0 0 0.925 ) with pressure. The average structure at 70 K does not show other indications of further phase transition.Y. Li and X. Du from Peking University are greatly acknowledged for growing and providing the CaMn7O12 crystals. D. Spahr and J. König from Goethe University are acknowledged for help with the single-crystal diffraction experiments. M.S. would like to acknowledge the financial support under the DFG-ANR Grant No. WI1232/41-1 and DFG GACR Project No. WI3320/3-1. V.M. and J.R.-F. thank the financial support from the Spanish Ministerio de Ciencia e Innovación (MICINN) for the Beatriz Galindo Program (BG20/000777) and for the Project No. PGC2018-097520- A-I00, respectively. DESY Photon Science is gratefully acknowledged. PETRA III at DESY is a member of the Helmholtz Association (HGF)

High-pressure compressibility and electronic properties of bismuth silicate Bi2SiO5\mathrm{Bi_2SiO_5} from synchrotron experiments and first-principles calculations

The high-pressure structural properties of bismuth oxide $\mathrm{Bi_2SiO_5}$ have been investigated up to 29 GPa using in situ powder synchrotron x-ray diffraction (XRD) and up to 50 GPa with density functional theory (DFT) calculations. We found a compressibility anomaly at about 20 GPa that is observed both in our XRD and DFT results. The rotation of the corner-connected SiO$_4$ tetrahedra produces a straightening of the silicate chains, yielding a lower compressibility above 20 GPa for the structure with straight chains. We analyzed the stereochemical activity of the Bi$^{3+}$ lone electron pair, which is found to decrease with increasing pressure, but it can still be identified in the calculated electron density difference maps at 50 GPa

Zr-containing layered double hydroxides: Synthesis, characterization, and evaluation of thermodynamic properties

Layered doubled hydroxides (LDH), consisting of positively charged octahedral brucite-type layers and interlayer anions, have been widely studied in the last decades because of their ability to control the mobility of various anions and cations in the environment. LDH may be relevant to the safety case of nuclear waste repositories due to their retention potential of anionic radionuclide species, for example 129I or 79Se. So far few studies were dedicated to Zr incorporation into LDH, which might be a relevant secondary phase in the repository environment due to the possible corrosion of Zr-bearing nuclear materials and the presence of 93Zr, a long-lived fission and activation product, in various nuclear waste streams. The focus of our study was to synthesize and characterize Cl-bearing Mg-Al-LDH (MgxAlyZrz(OH)2Cl(2x + 3y + 4z − 2)) with different Zr-content and to evaluate their thermodynamic properties, especially their solubility as a function of temperature. The LDH were synthesized by a coprecipitation method at temperatures between 298.15 and 343.15 K, aiming at Zr/(Zr + Al) ratios of 0.1 and 0.4, respectively. Our analytical techniques combining X-ray diffraction and scanning electron microscopy indicated that up to 5 mol% Zr were incorporated into the brucite layer of the LDH. At higher Zr concentrations the precipitation of an amorphous hydrous Zr-oxide was observed. The structural uptake of Zr was lower than the value reported in literature for CO32– bearing LDH, suggesting that the interlayer anions may play a role with regard to the Zr uptake in the brucite layer. At low Zr contents, well defined crystalline LDH with the composition Mg0.72Al0.22Zr0.025(OH)2Cl0.20 were obtained at all syntheses temperatures. The solubility of this LDH decreases slightly with temperature and the stoichiometric saturation constant was found to satisfy the Van't Hoff equation. The thermodynamic properties of the Zr LDH (Gibbs free energy of formation, ΔG°f) were determined by considering an approach based on solubility data and Gibbs energy minimization and a calorimetric approach. The enthalpy of formation (ΔH°f) and the lattice entropy (S°) of the Zr-LDH were determined using calorimetric measurements to be − 1181.01 ± 4.98 kJ mol− 1 and 83.9 J mol− 1 K− 1 respectively. Considering contribution of the configurational entropy, the standard entropy, S°, was evaluated at 97 ± 7 J mol− 1 K− 1. The ΔG°f for Mg0.72Al0.22Zr0.025(OH)2Cl0.20*0.69H2O obtained from experimental measurements and that predicted by theory were evaluated at − 1046 ± 7 and − 1046 ± 13 kJ mol− 1 respectively. Thus, the combination of solubility data and Gibbs energy minimization can be considered as good alternative for the evaluation of ΔG°f of LDH