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Here we present a comparative study of the magnetic and crystal chemical properties of two Co2+ containing garnets, NaCa2Co2V3O12 and CaY2Co2Ge3O12. Both phases exhibit the onset of antiferromagnetic order at 8K and 6K respectively, as well as field-induced transitions in their magnetization at 1T and around 11 T. We find these field-dependent transitions correspond to quantum critical points that result in the suppression of antiferromagnetic order and that these transitions can be clearly seen using magnetocapacitance measurements. Finally, we perform detailed crystal chemistry analyses and complimentary density functional theory calculations to show that changes in the local environment of the Co-ions are responsible for differences in the two magnetic structures and their respective properties.

Transition metal perovskite chalcogenides, a class of materials with rich tunability in functionalities, are gaining increased attention as candidate materials for renewable energy applications. Perovskite oxides are considered excellent n-type thermoelectric materials. Compared to oxide counterparts, we expect the chalcogenides to possess more favorable thermoelectric properties such as lower lattice thermal conductivity and smaller band gap, making them promising material candidates for high temperature thermoelectrics. Thus, it is necessary to study the thermal properties of these materials in detail, especially thermal stability, to evaluate their potential. In this work, we report the synthesis and thermal stability study of five compounds, \alpha-SrZrS$_3$, \beta-SrZrS$_3$, BaZrS$_3$, Ba$_2$ZrS$_4$, and Ba$_3$Zr$_2$S$_7$. These materials cover several structural types including distorted perovskite, needle-like, and Ruddlesden-Popper phases. Differential scanning calorimeter and thermo-gravimetric analysis measurements were performed up to 1200{\deg}C in air. Structural and chemical characterizations such as X-ray diffraction, Raman spectroscopy, and energy dispersive analytical X-ray spectroscopy were performed on all the samples before and after the heat treatment to understand the oxidation process. Our studies show that perovskite chalcogenides possess excellent thermal stability in air at least up to 600{\deg}C., Comment: 9 Figures

A structural phase transition from cubic $Fd\bar{3}m$ to tetragonal $I$4$_1$/$amd$ symmetry with $c/a >$ 1 is observed at $T_{\rm{S}}$ = 16 K in spinel GeCo$_2$O$_4$ below the N\'eel temperature $T_N$ = 21 K. Structural and magnetic ordering appear to be decoupled with the structural distortion occurring at 16 K while magnetic order occurs at 21 K as determined by magnetic susceptibility and heat capacity measurements. An elongation of CoO$_6$ octahedra is observed in the tetragonal phase of GeCo$_2$O$_4$. We present the complete crystallographic description of GeCo$_2$O$_4$ in the tetragonal $I$4$_1$/$amd$ space group and discuss the possible origin of this distortion in the context of known structural transitions in magnetic spinels. GeCo$_2$O$_4$ exhibits magnetodielectric coupling below $T_{\rm{N}}$. The related spinels GeFe$_2$O$_4$ and GeNi$_2$O$_4$ have also been examined for comparison. Structural transitions were not detected in either compound down to $T \approx$ 8 K. Magnetometry experiments reveal in GeFe$_2$O$_4$ a second antiferromagnetic transition, with $T_{\rm{N1}}$ = 7.9 K and $T_{\rm{N2}}$ = 6.2 K, that was previously unknown, and that bear a similarity to the magnetism of GeNi$_2$O$_4$.

In many ostensibly crystalline materials, unit-cell-based descriptions do not always capture the complete physics of the system due to disruption in long-range order. In the series of cobalt hydroxides studied here, Co(OH)$_{2-x}$(Cl)$_x$(H$_2$O)$_{n}$, magnetic Bragg diffraction reveals a fully compensated N\'eel state, yet the materials show significant and open magnetization loops. A detailed analysis of the local structure defines the aperiodic arrangement of cobalt coordination polyhedra. Representation of the structure as a combination of distinct polyhedral motifs explains the existence of locally uncompensated moments and provides a quantitative agreement with bulk magnetic measurements and magnetic Bragg diffraction.

Synchrotron X-ray total scattering studies of structural changes in rutile VO2 at the metal-insulator transition temperature of 340 K reveal that monoclinic and tetragonal phases of VO2 coexist in equilibrium, as expected for a first-order phase transition. No evidence for any distinct intermediate phase is seen. Unbiased local structure studies of the changes in V--V distances through the phase transition, using reverse Monte Carlo methods, support the idea of phase coexistence and point to the high degree of correlation in the dimerized low-temperature structure. No evidence for short range V--V correlations that would be suggestive of local dimers is found in the metallic phase., Comment: 4 pages, 5 figures

CoSeO$_4$ has a structure consisting of edge-sharing chains of Co$^{2+}$ octahedra which are held together by SeO$_4^{2-}$ tetrahedra via shared oxygen atoms at the edges of the octahedra. DC magnetization measurements indicate a transition to an ordered state below 30 K. Powder neutron diffraction refinements suggest an ordered state with two unique antiferrromagnetic chains within the unit cell. Isothermal magnetization measurements indicate a temperature-dependent field-induced magnetic transition below the ordering temperature. From neutron diffraction, we find this corresponds to a realignment of spins from the canted configuration towards the c-axis. The dielectric constant shows a change in slope at the magnetic ordering temperature as well as a quadratic dependence on the external magnetic field., Comment: 7 pages, 10 figures

Both amorphous and crystalline materials frequently exhibit low temperature specific heats in excess of what is predicted using the Debye model. The signature of this excess specific heat is a peak observed in $C/T^3$ \textit{versus} $T$. To understand the curious absence of long-range ordering of local distortions in the crystal structure of pyrochlore Bi$_2$Ti$_2$O$_7$, we have measured the specific heat of crystalline Bi$_2$Ti$_2$O$_7$ and related compounds. We find that the peak in $C/T^3$ versus $T$ in Bi$_2$Ti$_2$O$_7$ falls at a substantially lower temperature than other similar compounds, consistent with the presence of disorder. This thermodynamic evidence for disorder in crystalline Bi$_2$Ti$_2$O$_7$ is consistent with quenched configurational disorder among Bi lone pairs produced by geometrical frustration, which could represent a possible realization of "charge ice"., Comment: 4 Figures

CoSe$_2$O$_5$ has a crystal structure consisting of zig-zag chains of edge shared CoO$_6$ octahedra running along the c axis, with the chains separated by Se$_2$O$_5^{2-}$ units. Magnetic susceptibility measurements indicate a transition at 8.5 K to an ordered state. We investigate here the nature of this magnetic ordering using magnetization and specific heat measurements in addition to powder neuttron diffraction. A transition to long-range antiferromagnetic order is found below $T_N$ = 8.5 K as identified by magnetic susceptibility measurements and magnetic Bragg reflections, with a propagation vector $\mathbf{k}$ = 0. The magnetic structure shows that the moments align perpendicular to the c-axis, but with the spins canting with respect to the a axis by, alternately, $+8^\circ$ and $-8^\circ$. Interestingly, the low-field magnetic susceptibility does not show the anticipated cusp-like behavior expected for a well-ordered antiferromagnet. When the susceptibility is acquired under field-cooling conditions under a 10 kOe field, the the usual downturn expected for antiferromagnetic ordering is obtained. Heat capacity measurements at low temperatures indicate the presence of gapped behavior with a gap of 6.5 K., Comment: 5 pages, 5 figures

Time-of-flight neutron powder diffraction and specific heat measurements were used to study the nature of thermal expansion in rhenium trioxide, an electrically conducting oxide with cubic symmetry. The temperature evolution of the lattice parameters show that ReO3 can exhibit negative thermal expansion at low temperatures and that the transition from negative to positive thermal expansion depends on sample preparation; the single crystal sample demonstrated the highest transition temperature, 300 K, and largest negative value for the coefficient of thermal expansion, alpha = -1.1(1)x 10^-6 K^-1. For the oxygen atoms, the atomic displacement parameters are strongly anisotropic even at 15 K, indicative of a large contribution of static disorder to the displacement parameters. Further inspection of the temperature evolution of the oxygen displacement parameters for different samples reveals that the static disorder contribution is greater for the samples with diminished NTE behavior. In addition, specific heat measurements show that ReO3 lacks the low energy Einstein-type modes seen in other negative thermal expansion oxides such as ZrW2O8., Comment: 6 pages, 5 figures

The spinels CoB$_2$O$_4$ with magnetic Co$^{2+}$ ions on the diamond lattice A site can be frustrated because of competing near-neighbor ($J_1$) and next-near neighbor ($J_2$) interactions. Here we describe attempts to tune the relative strengths of these interactions by substitution on the non-magnetic B-site. The system we employ is CoAl$_{2-x}$Ga$_x$O$_4$, where Al is systematically replaced by the larger Ga, ostensibly on the B site. As expected, Ga substitution expands the lattice, resulting in Co atoms on the A-site being pushed further from one other and thereby weakening magnetic interactions. In addition, Ga distributes between the B and the A site in a concentration dependent manner displacing an increasing amount of Co from the A site with increasing $x$. This increased inversion, which is confirmed by neutron diffraction studies carried out at room temperature, affects magnetic ordering very significantly, and changes the nature of the ground state. Modeling of the magnetic coupling illustrates the complexity that arises from the cation site disorder., Comment: 9 pages, 10 figures

We present the magnetic properties of complete solid solutions of ZnCr$_2$O$_4$ and CoCr$_2$O$_4$: two well-studied oxide spinels with very different magnetic ground states. ZnCr$_2$O$_4$, with non-magnetic $d^{10}$ cations occupying the A site and magnetic $d^3$ cations on the B site, is a highly frustrated antiferromagnet. CoCr$_2$O$_4$, with magnetic $d^7$ cations (three unpaired electrons) on the A site as well, exhibits both N\'eel ferrimagnetism as well as commensurate and incommensurate non-collinear magnetic order. More recently, CoCr$_2$O$_4$ has been studied extensively for its polar behavior which arises from conical magnetic ordering. Gradually introducing magnetism on the A site of ZnCr$_2$O$_4$ results in a transition from frustrated antiferromagnetism to glassy magnetism at low concentrations of Co, and eventually to ferrimagnetic and conical ground states at higher concentrations. Real-space Monte-Carlo simulations of the magnetic susceptibility suggest that the first magnetic ordering transition and features of the susceptibility across $x$ are captured by near-neighbor self- and cross-couplings between the magnetic A and B atoms. We present as a part of this study, a method for displaying the temperature dependence of magnetic susceptibility in a manner which helps distinguish between compounds possessing purely antiferromagnetic interactions from compounds where other kinds of ordering are present., Comment: 10 pages, 5 figures, 1 table