High-field Transition Research Articles

An experimental study on the role of F−, PO43−, Cl− and SO42− ligands in the natrocarbonatite-nephelinite system at 850 °C and 0.1 GPa

Carbonatites and their comagmatic silicate rocks related deposit provide significant resources of rare earth elements (REEs), niobium (Nb) and other elements such as U, Th, Mo, V, Ba, Sr, etc. However, the genesis of mineralization, especially for REEs and Nb, in carbonatite remains enigmatic. Previous liquid immiscibility experiments have demonstrated that both REEs and Nb are preferentially enriched in the silicate conjugate instead of carbonate melts under anhydrous conditions. Nevertheless, ligands other than carbonate ion appear to be abundant due to ubiquity of apatite, baryte, celestine, fluorite and sodalite in carbonate–silicate magmatic systems. Here, we experimentally investigate the trace element partitioning between natrocarbonate and silicate (nephelinite) melts in systems doped with varying amounts of additional F−, PO43−, Cl−, and SO42− ligands (0, 2, 4 and 6 wt%) to understand and constrain the role of ligands.The experiments were conducted at 850 °C and 0.1 GPa using rapid quench cold-seal pressure vessels (CSPVs). A comparison of experimental partition coefficients in this study reveals that the significant amounts F− and PO43− incorporated in the silicate melts can increase the D values for REE by influencing melt structure (DLaCM/SM = 0.85–7.42). In contrast, irrespective of the amount of added Cl− and SO42−, DCM/SM is not affected significantly by these species and the DREECM/SM values remain always lower than 1 (DLaCM/SM = 0.12–0.40). Notably, the DNbCM/SM values are all <1, with only one exception containing 6 wt% F. Besides, in all the investigated systems, Ba, Sr, Mo, V, Cs, Rb and Li preferentially partition into the conjugate carbonate melt. All the high field strength elements (Pb, Th, U, Zr, Hf, Nb, Ta), transition metals (Mn, Co, Cu, Zn) and common network formers (Ga, Ge) essentially partition into the silicate melt.

Cleavable crystals, crystal structure, and magnetic properties of the NbFe1+xTe3 layered van der Waals telluride.

Transition metal-based two-dimensional nanomaterials with competing magnetic states are at the cutting edge of spintronic and low-power memory devices. In this paper, we present a Fe-rich NbFe1+xTe3 layered telluride (x ≈ 0.5), which shows an interplay of spin-glass and antiferromagnetic states below the Néel temperature of 179 K. The compound has a layered crystal structure, where the NbFeTe3 layers are terminated by the Te atoms and van der Waals gaps. Bulk single crystals grown by chemical vapor transport reactions possess the (1̄01) cleavage plane suitable for the exfoliation of two-dimensional nanomaterials. Combination of high-resolution transmission electron microscopy and powder X-ray diffraction reveals the zigzag ladders of Fe atoms inside the structural layers, as well as complementary zigzag chains of the partially occupied Fe positions in the interstitial region. Fe atoms carry large effective magnetic moment of 4.85(3)μB per atom in the paramagnetic state yielding intriguing magnetic properties of NbFe1+xTe3. They include frozen spin-glass state at low temperatures and spin-flop transition in high magnetic fields indicating promising flexibility of the magnetic system and its potential control by magnetic field or gate tuning in the spintronic devices and heterostructures.

Field-orientation dependence of quantum phase transitions in the S=12 triangular-lattice antiferromagnet Ba3CoSb2O9

Ba$_3$CoSb$_2$O$_9$ approximates the two-dimensional spin-1/2 triangular-lattice Heisenberg antiferromagnet. This compound displays magnetic-field-induced quantum phase transitions, including the 1/3-magnetization-plateau, but its magnetization processes for the magnetic field $H$ parallel and perpendicular to the $c$ axis are different due to the weak easy-plane anisotropy and the weak interlayer antiferromagnetic exchange interaction. To elucidate how the quantum phase transitions change between these two field directions, we measured the field-angle dependence of the magnetization process in Ba$_3$CoSb$_2$O$_9$ using pulsed high magnetic fields. We compared obtained magnetic field-field angle phase diagram with those obtained by the large-size cluster mean-field method combined with a scaling scheme and the semiclassical theory. We also found a narrow 1/3-magnetization plateau and a high-field transition with a small magnetization jump for $H\,{\parallel}\,c$, not observed in the previous studies.

Fermi-surface reconstruction at the metamagnetic high-field transition in uranium mononitride

We report on the electronic and thermodynamic properties of the antiferromagnetic metal uranium mononitride with a N\'eel temperature $T_N\approx 53\,$K. The fabrication of microstructures from single crystals enables us to study the low-temperature metamagnetic transition at approximately $58\,$T by high-precision magnetotransport, Hall-effect, and magnetic-torque measurements. We confirm the evolution of the high-field transition from a broad and complex behavior to a sharp first-order-like step, associated with a spin flop at low temperature. In the high-field state, the magnetic contribution to the temperature dependence of the resistivity is suppressed completely. It evolves into an almost quadratic dependence at low temperatures indicative of a metallic character. Our detailed investigation of the Hall effect provides evidence for a prominent Fermi-surface reconstruction as the system is pushed into the high-field state.

Direct Observation of Fractal-Dimensional Percolation in the 3D Cluster Dynamics of a Ferroelectric Supercrystal.

We perform percolation analysis of crossed-polarizer transmission images in a biased nanodisordered bulk KTN:Li perovskite. Two distinct percolative transitions are identified at two electric field thresholds. The low-field transition involves a directional fractal chain of dimension D=1.65, while the high-field transition has a dimension D>2. Direct cluster imaging in the volume is achieved using high-resolution orthographic 3D projections based on giant refraction. Percolation is attributed to a full-3D domain reorientation that mediates the transition from a ferroelectric supercrystal state to a disordered domain mosaic.

NMR study of magnetic structure and hyperfine interactions in the binary helimagnet FeP

We report a detailed study of the ground state helical magnetic structure in monophosphide FeP by means of ${}^{31}$P NMR spectroscopy. We show that the zero-field NMR spectrum of the polycrystalline sample provides strong evidence of an anisotropic distribution of local magnetic fields at the P site with substantially lower anharmonicity than that found at the Fe site by M\"{o}ssbauer spectroscopy. From field-sweep ${}^{31}$P NMR spectra we conclude that a continuous spin-reorientation transition occurs in an external magnetic field range of 4 - 7 T, which is also confirmed by specific-heat measurements. We observe two pairs of magnetically inequivalent phosphorus positions resulting in a pronounced four-peak structure of the single crystal ${}^{31}$P NMR spectra characteristic of an incommensurate helimagnetic ground state. We revealed a spatial redistribution of local fields at the P sites caused by Fe spin-reorientation transition in high fields and developed an effective approach to account for it. We demonstrate that all observed ${}^{31}$P spectra can be treated within a model of an isotropic helix of Fe magnetic moments in the ($ab$)-plane with a phase shift of 36$^{\circ}$ and 176$^{\circ}$ between Fe1-Fe3 (Fe2-Fe4) and Fe1-Fe2 (Fe3-Fe4) sites, respectively, in accordance with the neutron scattering data.

Polybaric/polythermal magma transport and trace element partitioning recorded in single crystals: A case study of a zoned clinopyroxene from Mt. Etna

We present elemental maps and intra-crystal compositional profiles conducted on a representative clinopyroxene phenocryst from the 1974 eccentric lava flows at Mt. Etna volcano (Sicily, Italy). The eruption was fed by deep-seated and primitive magmas ascending through pathways bypassing the central volcanic conduits. These magmas show MgO and Cr contents higher (and REE + Y lower) than those characterizing younger and more evolved eruptions, albeit the bulk rock compositions of both primitive and more evolved products are invariably classified as trachybasalts in the TAS (total alkali vs. silica) diagram. Mafic recharge episodes are recorded by the complex textural features of the clinopyroxene, with a subrounded core enclosed within a concentrically zoned mantle. The core is enriched in Mg + Fe2++Na and depleted in Fe3++Ca relative to the mantle. The jadeite (Jd) component decreases from core to mantle and is counterbalanced by higher Ca-Tschermak (CaTs) contents, as the number of TAl cations in tetrahedral coordination increases. The Jd-rich core incorporates high proportions of rare earth elements and Y (REE + Y) and low concentrations of high field strength elements (HFSE) and transition elements (TE, such as Ni, Cr and Sc), whereas the opposite occurs for the CaTs-rich mantle. The decoupling of REE + Y and HFSE argues against simple changes in melt composition and indicates an additional mechanism driving trace element zonations. Thermobarometric calculations indicate that the early-formed Jd-rich core equilibrated with the host magma at mantle depths (750–950 MPa and 1190–1210 °C), whereas the later CaTs-rich mantle formed at shallower crustal levels (400–700 MPa and 1150–1180 °C) after magma recharge. Quantitative modeling of apparent cation partitioning between clinopyroxene and melt (Di) indicates that DHFSE increase from the Jd-rich core to the CaTs-rich mantle. In contrast, DREE+Y increase up to one order of magnitude at the Jd-rich core due to the enhanced stability of an Na0.5REE + Y0.5MgSiO6 end-member. We infer that compositional changes in clinopyroxene due to the different P-T conditions of the plumbing system may control the concentrations of REE + Y in residual melts derived after partial crystallization and differentiation of primitive magmas, such as those feeding the 1974 eccentric eruption. On this basis, we use DREE+Y measured across the core-mantle interface to constrain the geochemical evolution of recent 2000–2013 magmas at Mt. Etna volcano by Rayleigh fractional crystallization. Results indicate that magma dynamics proceed via a stepwise polybaric-polythermal process accounting for 1) crystallization of Jd-rich clinopyroxenes at high-P, high-T conditions, 2) upward migration of crystal-bearing magmas due to replenishment phenomena with input of fresh magmas and 3) crystallization of CaTs-rich clinopyroxene in low-P, low-T reservoirs. The resulting total amount (~40 vol%) of clinopyroxene fractionated agrees with geophysical data suggesting the presence of highly crystalline magmatic bodies at shallow to intermediate crustal levels below Mt. Etna.

Provenance and tectonic setting of the Lower Cambrian Niutitang formation shales in the Yangtze platform, South China: Implications for depositional setting of shales

Geochemical compositions of the Lower Cambrian Niutitang Formation shales in the southeastern Yangtze Platform margin were investigated for provenance, tectonic setting, and depositional environment. The shale samples are characterized by higher abundances of large ion lithophile elements (Cs, Ba, and Pb), lower abundances of high field strength elements (Cr, Sc, and Co) and transition elements (Th, Zr, Hf, Nb, and Ta) relative to average shale. North American shale composition (NASC) -normalized rare earth element (REE) patterns are observed, with negative Ce anomalies, negative Eu anomalies, and positive Y anomalies. The chemical index of alteration (CIA) varies from 68.67–74.93. Alkali and alkaline element contents and CIA values suggest that the source rocks have undergone moderate weathering. The index of compositional variability (ICV), Zr/Sc and Th/Sc ratios vary from 0.53 to 1.07, 5.31 to 8.18 and 0.52–1.02, respectively. ICV values and relationships between Zr/Sc and Th/Sc ratios indicate negligible sedimentary recycling. The Al2O3/TiO2 (14–26) and TiO2/Zr (56–77) ratios imply that the source rocks of the investigated shales had intermediate igneous compositions. However, Cr/V ratios and a La/Th–Hf discrimination diagram suggest that the intermediate compositional signal of the source rocks was derived from a mixture of 75% mafic and 25% felsic igneous rocks rather than intermediate igneous rocks. The major source was the Jiangnan continental island arc with bimodal igneous rocks, lying to the south of the study area, together with a contribution from granites and gneisses uplifted and eroded in the Yangtze Block. Discrimination of tectonic setting using major and trace elements indicates that the source rocks originated in a transitional setting from active continental to passive margin, consistent with the failed intracontinental rift model for the evolution of the South China plate. The Niutitang Formation shales were deposited in a rift basin setting under conditions of anoxic bottom water in a redox-stratified water column, with organic-rich shales prospective for shale-gas production being found in deep-water downslope and basin environments rather than the shallow-water shelf.

Hyperactivation of the Frontal Control Network Revealed by Symptom Provocation in Obsessive-Compulsive Disorder Using EEG Microstate and sLORETA Analyses

The aim of this study was to investigate the changes of brain electric field induced by symptom provocation in patients with obsessive-compulsive disorder (OCD) in comparison to healthy controls in the resting state. For this purpose, EEG recordings in conditions of initial rest, clean control, symptom provocation by imaginal exposure, and final rest were used for computing spatiotemporal activity characteristics based on microstate segmentation. Within-group comparisons were significant for the symptom provocation condition: OCD showed high global field power (GFP) and transition rates into a medial frontal microstate, whereas healthy controls showed high frequency of occurrence and high percent of dwelling time for a medial occipitoparietal microstate. Between-group comparisons demonstrated significantly lower GFP and dwelling time for the medial occipitoparietal microstate in OCD in several conditions including initial rest and symptom provocation. In addition, OCD compared to healthy controls showed significant instability of the medial occipitoparietal microstate, with high preference for transitions into the medial frontal microstate. In conclusion, during rest and symptom provocation, OCD patients make preferential use of a medial frontal brain network, with concomitant reduction of use of a medial occipitoparietal network, as shown by dwelling times, explained variance, and dynamic transition rates. These findings support the idea of a possible biological marker for OCD, which might correspond to pathological hyperactivation of the frontal control network.

Unusual magnetoelectric memory and polarization reversal in the kagome staircase compound Ni3V2O8

We study the electric polarization of the kagome staircase $\mathrm{N}{\mathrm{i}}_{3}{\mathrm{V}}_{2}{\mathrm{O}}_{8}$ in magnetic fields up to 30 T and report a magnetoelectric memory effect controlled by bias electric fields. The explored ferroelectric phase in $19--24\phantom{\rule{0.16em}{0ex}}\mathrm{T}$ is electrically controlled, whereas the ferroelectric phase in $2--11\phantom{\rule{0.16em}{0ex}}\mathrm{T}$ exhibits unusual memory effects. We determine a characteristic critical magnetic field ${\mathbit{H}}_{3}=11\phantom{\rule{0.16em}{0ex}}\mathrm{T}$, below which strong memory exists and the polarization is frozen even in opposite bias fields. But when magnetic fields exceed ${\mathbit{H}}_{3}$, the frozen polarization is released and polarization reversal appears by tuning bias electric fields. We ascribe these phenomena to the pinning-depinning mechanism: nucleation and the accompanying pinning of chiral domain walls cooperatively induce the frozen behavior; the polarization reversal results from the depinning through the ferroelectrtic-to-paraelectric phase transition in high magnetic fields. Our experimental results reveal that the first-order phase transition plays an important role in these unusual memory effects.

Textures and U-W-Sn-Mo signatures in hematite from the Olympic Dam Cu-U-Au-Ag deposit, South Australia: Defining the archetype for IOCG deposits

The textural characteristics and trace element geochemistry of hematite with U-W-Sn-Mo signatures from the Cu-U-Au-Ag orebody at Olympic Dam, South Australia, are documented. Olympic Dam is the archetype for iron-oxide copper–gold (IOCG) deposits where hematite is by far the most abundant mineral in the orebody. The deposit is located within hematite-bearing breccias (>5% Fe) hosted by the ∼1.6 Ga Roxby Downs Granite (RDG). Although such breccias are mostly derived from RDG, they also include volcanic clasts and sedimentary rocks. Samples cover the ∼6 km strike length and ∼2 km vertical extent of mineralisation, including hematite from the aforementioned lithologies. Hematite with U-W-Sn-Mo (‘granitophile’ elements) signatures is recognised throughout all lithologies and parts of the deposit. Hematite enriched in granitophile elements is represented by a variety of textures, of which zoned hematite, defined by oscillatory zonation patterns, is the most prominent and can be tied to the age of the RDG, and thus initiation of the IOCG system as confirmed by published U-Pb geochronology. Other categories of hematite with granitophile signatures include hematite resulting from replacement of pre-existing minerals (e.g., carbonates and feldspars), as well as replacement of previous oscillatory-zoned hematites. Matrix and vacuole filling hematite from volcanoclastic-dominated intervals also carry ‘granitophile’ signatures. In addition, some colloform types which likely post-date primary IOCG mineralisation are also rich in ‘granitophile’ elements. Trace element mapping and spot analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) defines complex trace element signatures of hematite, which, in addition to the ‘granitophile’ elements, also comprise rare earth elements, high field strength elements, chalcogens and transition metals.The distinct geochemical signature, characterised by enrichment in the ‘granitophile’ elements (up to wt% levels of U and W within individual zones, and up to thousands of ppm Mo and Sn) prevails throughout the hematite in the deposit irrespective of textures. Iron-oxides have been repeatedly formed, reworked and overprinted by subsequent cycles of brecciation, fluid-mineral reaction, remobilization, element redistribution and recrystallisation. Coupled dissolution-replacement reactions are discussed as having played a major role in the modification of textural and geochemical patterns in hematite, but also allow for widespread preservation of primary geochemical signatures. Despite its simple chemistry, the crystal-structural modularity of hematite can adapt and retain evolving fluid signatures. The reported trace element signatures are fully concordant with conceptual frameworks for the genesis of IOCG systems, and may be an inherent, albeit hitherto under-reported characteristic of other IOCG systems. Hematite is probably by far the most important W-, Sn- and Mo-bearing phase in the deposit by mass.

Frustrated honeycomb-lattice bilayer quantum antiferromagnet in a magnetic field

Frustrated bilayer quantum magnets have attracted attention as flat-band spin systems with unconventional thermodynamic properties. We study the low-temperature properties of a frustrated honeycomb-lattice bilayer spin-12 isotropic (XXX) Heisenberg antiferromagnet in a magnetic field by means of an effective low-energy theory using exact diagonalizations and quantum Monte Carlo simulations. Our main focus is on the magnetization curve and the temperature dependence of the specific heat indicating a finite-temperature phase transition in high magnetic fields.

Ultrafast Magnetism of a Ferrimagnet across the Spin-Flop Transition in High Magnetic Fields.

We show that applying magnetic fields up to 30T has a dramatic effect on the ultrafast spin dynamics in ferrimagnetic GdFeCo. Upon increasing the field beyond a critical value, the dynamics induced by a femtosecond laser excitation strongly increases in amplitude and slows down significantly. Such a change in spin response is explained by different dynamics of the Gd and FeCo magnetic sublattices following a spin-flop phase transition from a collinear to a noncollinear spin state.

Stability of High-Density Two-Dimensional Excitons against a Mott Transition in High Magnetic Fields Probed by Coherent Terahertz Spectroscopy.

We have performed time-resolved terahertz absorption measurements on photoexcited electron-hole pairs in undoped GaAs quantum wells in magnetic fields. We probed both unbound- and bound-carrier responses via cyclotron resonance and intraexciton resonance, respectively. The stability of excitons, monitored as the pair density was systematically increased, was found to dramatically increase with increasing magnetic field. Specifically, the 1s-2p_{-} intraexciton transition at 9T persisted up to the highest density, whereas the 1s-2p feature at 0T was quickly replaced by a free-carrier Drude response. Interestingly, at 9T, the 1s-2p_{-} peak was replaced by free-hole cyclotron resonance at high temperatures, indicating that 2D magnetoexcitons do dissociate under thermal excitation, even though they are stable against a density-driven Mott transition.

Probing the Influence of Dielectric Environment on Excitons in Monolayer WSe2: Insight from High Magnetic Fields.

Excitons in atomically thin semiconductors necessarily lie close to a surface, and therefore their properties are expected to be strongly influenced by the surrounding dielectric environment. However, systematic studies exploring this role are challenging, in part because the most readily accessible exciton parameter-the exciton's optical transition energy-is largely unaffected by the surrounding medium. Here we show that the role of the dielectric environment is revealed through its systematic influence on the size of the exciton, which can be directly measured via the diamagnetic shift of the exciton transition in high magnetic fields. Using exfoliated WSe2 monolayers affixed to single-mode optical fibers, we tune the surrounding dielectric environment by encapsulating the flakes with different materials and perform polarized low-temperature magneto-absorption studies to 65 T. The systematic increase of the exciton's size with dielectric screening, and concurrent reduction in binding energy (also inferred from these measurements), is quantitatively compared with leading theoretical models. These results demonstrate how exciton properties can be tuned in future 2D optoelectronic devices.

Successive Magnetic-Field-Induced Transitions and Colossal Magnetoelectric Effect in Ni_{3}TeO_{6}.

We report the discovery of a metamagnetic phase transition in a polar antiferromagnet Ni_{3}TeO_{6} that occurs at 52 T. The new phase transition accompanies a colossal magnetoelectric effect, with a magnetic-field-induced polarization change of 0.3 μC/cm^{2}, a value that is 4 times larger than for the spin-flop transition at 9 T in the same material, and also comparable to the largest magnetically induced polarization changes observed to date. Via density-functional calculations we construct a full microscopic model that describes the data. We model the spin structures in all fields and clarify the physics behind the 52 T transition. The high-field transition involves a competition between multiple different exchange interactions which drives the polarization change through the exchange-striction mechanism. The resultant spin structure is rather counterintuitive and complex, thus providing new insights on design principles for materials with strong magnetoelectric coupling.

Electron spin echo and spin relaxation of low-symmetry Mn2+-complexes in ammonium oxalate monohydrate single crystal

Pulse EPR experiments were performed on low concentration Mn2+ ions in ammonium oxalate monohydrate single crystals at X-band, in the temperature range 4.2–60K at crystal orientation close to the D-tensor z-axis. Hyperfine lines of the resolved spin transitions were selectively excited by short nanosecond pulses. Electron spin echo signal was not observed for the low spin transition (+5/2↔+3/2) suggesting a magnetic field threshold for the echo excitation. Echo appears for higher spin transitions with amplitude, which grows with magnetic field. Opposite behavior displays amplitude of echo decay modulations, which is maximal at low field and negligible for high field spin transitions. Electron spin–lattice relaxation was measured by the pulse saturation method. After the critical analysis of possible relaxation processes it was concluded that the relaxation is governed by Raman T7-process. The relaxation is the same for all spin transitions except the lowest temperatures (below 20K) where the high field transitions (−3/2↔−1/2) and (−5/2↔−3/2) have a slower relaxation rate. Electron spin echo dephasing is produced by electron spectral diffusion mainly, with a small contribution from instantaneous diffusion for all spin transitions. For the highest field transition (−5/2↔−3/2) an additional contribution from nuclear spectral diffusion appears with resonance type enhancement at low temperatures.

An experimental study of trace element partitioning between augite and Fe-rich basalts

Aluminous titanium-rich hedenbergite and Fe-rich augite were experimentally produced at 1050–1220°C and 0.8–2.2GPa. Major element compositions are analogous to clinopyroxene from layered intrusions, angrites, nakhlites, and late-stage lunar magma ocean cumulates. Trace element concentrations in pyroxene and coexisting melt were measured by laser ablation inductively coupled plasma mass spectrometry for rare earth elements (REE), high field strength elements (HFSE), transition metals, and large-ion lithophile elements. REE, HFSE, and transition metal partition coefficients (Ds) are tightly correlated with the cation abundance of Fe on the pyroxene M1 site (XFeM1), and also correlated with Al on the tetrahedral site (XAlT). Parameterized lattice-strain models were developed to predict REE and HFSE partition coefficients as functions of temperature and pyroxene composition (XAlT or XFeM1). The parameterized models can be used to calculate REE and HFSE partition coefficients for Fe-rich high-Ca pyroxene. We calculated partition coefficients for clinopyroxene derived from modeled end-stage lunar magma ocean cumulate compositions and observe a factor of 3 variation in clinopyroxene-melt REE partition coefficients. Using representative nakhlite clinopyroxene core and rim compositions we calculated partition coefficients and observed a factor of 4 variability in clinopyroxene-melt REE partition coefficients. HFSE partition coefficients are even more sensitive to composition, showing variations of a factor of 4 for lunar late cumulates and an order of magnitude for nakhlites. The strong dependence of REE and HFSE partitioning on composition necessitates careful selection of appropriate partition coefficients for Fe-rich systems.

The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth

We present the variation in trace element partition coefficients measured at the interface between rapidly cooled clinopyroxene crystals and co-existing melts. Results indicate that, as the cooling rate is increased, clinopyroxene crystals are progressively depleted in Si, Ca and Mg counterbalanced by enrichments in Al (mainly tetrahedral Aliv), Na and Ti. Partition coefficients (Ds) for rare earth elements (REE), high field strength elements (HFSE) and transition elements (TE) increase with increasing cooling rate, in response to clinopyroxene compositional variations. The entry of REE into the M2 site is facilitated by a coupled substitution where either Na substitutes for Ca on the M2 site or Aliv substitutes for Si in the tetrahedral site. The latter substitution reflects an increased ease of locally balancing the excess charge at M2 as the number of surrounding Aliv atoms increases. Due to the lower concentration of Ca in rapidly cooled clinopyroxenes, divalent large ion lithophile elements (LILE) on M2 decrease at the expense of monovalent cations. Conversely, higher concentrations of HFSE and TE on the M1 site are facilitated as the average charge on this site increases with the replacement of divalent-charged cations by Alvi. Although crystallization kinetics modify clinopyroxene composition, deviations from equilibrium partitioning are insufficient to change the tendency of a trace element to be compatible or incompatible. Consequently, there are regular relationships between ionic radius, valence of the trace element and D. At both equilibrium and cooling rate conditions, Ds for isovalent cations define parabola-like curves when plotted against ionic radius, consistent with the lattice strain model, demonstrating that the partitioning of trace elements is driven by charge balance mechanisms; cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations.

High-field magnetic phase diagram of CsCoCl3 revised

Abstract A fine structure of high-field magnetization curves of CsCoCl 3 and related compounds is discussed. It is shown that a precursor of a high-field phase transition originates from nucleation of an intermediate high-field ferrimagnetic (IFM) phase. Since the IFM state is degenerate its growth starting from few nucleation centers gives rise to domain walls formation. Their creep also makes a contribution to the magnetization dynamics similar to slow relaxation in Ca 3 Co 2 O 6 . An experimental verification of the model is proposed.