Electronic structure calculations are carried out to estimate the heats of formation of rare-earth orthophosphates from their oxides. The calculated heats of formation are systematically about 40 kJ/mol less exothermic than the measured values. Based on estimated corrections for zero-point energies and H(298.15)-H(0), the discrepancy is almost entirely electronic in origin. The decreasingly exothermic ΔHfox with decreasing ionic radius (i.e. LaPO4 more exothermic than ScPO4) results from the higher charge localization on the oxide anion (O2-) relative to the phosphate anion (PO43-). The lattice energy, of course, becomes more negative with decreasing ionic radius for both oxide and phosphate phases, but does so more rapidly for the oxide, making the reaction less exothermic as ionic radius becomes smaller. This effect should carry over to ΔHfox other oxyacids, such as silicates and sulfates.
Unveiling the potential of NdPO4 magnetocaloric phases in cryogenic refrigeration
International University of Rabat（拉巴特国际大学）；Institut Quantique, Université de Sherbrooke（舍布鲁克大学量子研究所）；Université de Lorraine, CNRS, IJL（洛林大学、法国国家科学研究中心、IJL）；MAScIR, Mohammed VI Polytechnic University（马斯基尔研究所、穆罕默德六世polytechnic大学）
We provide accurate projected augmented wave (PAW) datasets for rare-earth (RE) elements with some suggested Hubbard U values allowing efficient plane-wave calculations. Solid state tests of generated datasets were performed on rare-earth nitrides. Through density of state (DOS) and equation of state (EoS) comparisons, generated datasets were shown to yield excellent results comparable to highly accurate all-electron full-potential linearized augmented plane-wave plus local orbital (FLAPW+LO) calculations. Hubbard U values for trivalent RE ions are determined according to hybrid functional cal…
Following the finite-temperature ab initio calculation framework based on the relativistic disordered local moments, we computationally demonstrate the possibility of doping-enhanced coercivity at high-temperatures, taking YCo$_5$ as a working material in order to extract the $3d$-electron part of the electronic structure of the rare-earth permanent magnets. Alkaline-earth dopants are shown to be the candidates to realize the proposed phenomenon.
We present an application of a high-throughput search of new rare-earth free permanent magnets focusing on 3d-5d transition metal compounds. The search involved a part of the ICSD database (international crystallographic structural database), together with tailored search criteria and electronic structure calculations of magnetic properties. Our results suggest that it possible to find candidates for rare-earth free permanent magnets using a data-mining/data-filtering approach. The most promising candidates identified here are Pt$_2$FeNi, Pt$_2$FeCu, and W$_2$FeB$_2$. We suggest these material…
We present an improved analysis of the phase transitions in rare earth superconductor using Ginzburg-Landau theory. Our work is based on the systematic study of critical field and superconducting order parameter in the presence of localized magnet due to rare-earth atom. We present the different phases that can occur and analyze the conditions of phase transition from the normal phase to the coexistence phase of antiferromagnetism and super-conductivity. We calculate the critical field and Ginzburg-Landau parameters to show the coexisting property. We compare our theoretical results with exist…
In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.
The dielectric properties and phase grouping of Rare earth Neodymium Zinc Titanate (NZT) was investigated in this research. The result shows that it is distrustful to be a stable perovskite structure, in fact something comparable to Ilmenite structure, however the further research shows that the monoclinic structure can be purposed for NZT. The Modelling and simulation were used in this research to define the atomic position and crystal structure of NZT. These compositions have promising dielectric properties and can be used in microwave telecommunications.
Rare-earth titanates RTiO$_3$ are Mott insulators displaying a rich physical behavior, featuring most notably orbital and spin orders in their ground state. The origin of their ferromagnetic to antiferromagnetic transition as a function of the size of the rare-earth however remains debated. Here we show on the basis of symmetry analysis and first-principles calculations that although rare-earth titanates are nominally Jahn-Teller active, the Jahn-Teller distortion is negligible and irrelevant for the description of the ground state properties. At the same time, we demonstrate that the combinat…
Rare earth contributions to the X-ray magnetic circular dichroism at the Co K edge in rare earth-cobalt compounds investigated by multiple-scattering calculations
The Curie temperature ($T_C$) of binary alloy compounds consisting of 3$d$ transition-metal and 4$f$ rare-earth elements is analyzed by a machine learning technique. We first demonstrate that nonlinear regression can accurately reproduce $T_C$ of the compounds. The prediction accuracy for $T_C$ is maximized when five to ten descriptors are selected, with the rare-earth concentration being the most relevant. We then discuss an attempt to utilize a regression-based model selection technique to learn the relation between the descriptors and the actuation mechanism of the corresponding physical ph…
We have studied the structural stability of Sc-substituted rare earth (R) ferrites R1-xScxFeO3, and constructed a structural phase diagram for different R and x. While RFeO3 and ScFeO3 adopt the orthorhombic and the bixbyite structure respectively, the substituted compound R1-xScxFeO3 may be stable in a different structure. Specifically, for R0.5Sc0.5FeO3, the hexagonal structure can be stable for small R, such as Lu and Yb, while the garnet structure is stable for larger R, such as Er and Ho. The formation of garnet structure of the R0.5Sc0.5FeO3 compounds which requires that Sc occupies both…
The development of permanent magnets containing less or no rare-earth elements is linked to profound knowledge of the coercivity mechanism. Prerequisites for a promising permanent magnet material are a high spontaneous magnetization and a sufficiently high magnetic anisotropy. In addition to the intrinsic magnetic properties the microstructure of the magnet plays a significant role in establishing coercivity. The influence of the microstructure on coercivity, remanence, and energy density product can be understood by {using} micromagnetic simulations. With advances in computer hardware and num…
The synthesis, structural description, temperature dependent magnetic susceptibilities and field dependent magnetizations of a series of rare earth garnets of the form Li3RE3Te2O12 (RE = Y, La, Pr, Nd, Sm-Lu) are reported. The structure of Li3Dy3Te2O12 is refined from powder X-ray diffraction data. The field dependent magnetizations saturate for some of the members by 9 Tesla at 2 K. Of particular interest for further study in this family is the behavior of the Pr, Tb, Dy and Yb garnets.
We study magneto-transport phenomena in two rare-earth doped topological insulators, SmxFexSb2-2xTe3 and SmxBi2-xTe2Se single crystals. The magneto-transport behaviours in both compounds exhibit a systematic crossover between weak anti-localization (positive magnetoresistance) and weak localization (negative magnetoresistance) with changes in temperatures and magnetic fields. The weak localization is caused by rare-earth-doping induced magnetization, and the weak anti-localization originates from topologically protected surface states. The transition between weak localization and weak anti-loc…
Ultrafast spin control plays a pivotal role in condensed matter physics. In this study, we analyzed the macroscopic magnetization of the PrFe0.1Cr0.9O3 system by molecular field model fitting. And the whole process of system spin reorientation is accurately calculated in the fitting process. It is found that, unlike the rare-earth perovskites we have previously studied, PrFe0.1Cr0.9O3 exhibits spin-reversion properties during the reorientation process. This research will lay a theoretical foundation for precise spin control in the future.
We present a data set of calculated Curie temperatures for the main-phase compounds of rare-earth permanent magnets. We employ ab initio electronic structure calculations for the itinerant ferromagnetism and an effective spin model for the finite-temperature magnetism. Curie temperatures are derived on the basis of a classical Heisenberg model mapped via Liechtenstein's formula for atomic-pair-wise exchange couplings. Relative trends with respect to the species of rare-earth elements in calculated Curie temperatures for R2Fe14B are in agreement with experimental trends. Quantitative comparison…
It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of anion vacancy in the nearest neighborhood, as was reported in the previous paper [Journal of Physics and …
We report the effect of partial substitution of Dy-site by rare-earths (R=Gd, Er and La)on the magnetic and magnetocaloric behavior of a mixed metal oxide DyFe0.5Cr0.5O3.Structural studies reveal that substitution of Dy by R has a minimal influence on the crystal structure. Magnetic and heat capacity studies show that the magnetic transition around 121 K observed for DyFe0.5Cr0.5O3 remains unchanged with rare-earth substitution, whereas the lower magnetic transition temperature is suppressed/enhanced by magnetic/non-magnetic substitution. In all these compounds, the second order nature of magn…
Magneto-optical spectroscopy in fields up to 30 Tesla reveals anomalies in the equilibrium and ultrafast magnetic properties of the ferrimagnetic rare-earth-transition metal alloy TbFeCo. In particular, in the vicinity of the magnetization compensation temperature, each of the magnetizations of the antiferromagnetically coupled Tb and FeCo sublattices show triple hysteresis loops. Contrary to state-of-the-art theory, which explains such loops by sample inhomogeneities, here we show that they are an intrinsic property of the rare-earth ferrimagnets. Assuming that the rare-earth ions are paramag…
The perovskite rare-earth (RE) chromite series (RE)CrO3 (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb, Lu) has been synthesized in our laboratory using microwave techniques. In this work we will demonstrate how X-ray diffraction (XRD), Rietveld refinement of XRD pattern and complementary High Resolution Transmission Electron Microscopy (HRTEM) were used to confirm that the desired crystal structure had been formed. Field-emission scanning electron microscopy (FE-SEM) gave clear indications of the shapes and sizes of the powder crystallites. Magnetization measurement data was foun…
The easy axis of the magnetic response of the conduction electrons of yttrium and rare earths
我们描述了一个第一性原理计算的静态，顺磁性，自旋磁化率的金属与相对论效应，如自旋轨道耦合。这给出了所施加的调制磁场的方向，以使其响应最大化。这个易磁化轴取决于调制的波矢量q。对于h. c. p.钇，我们发现在q=（0，0，0.57）pi/c处的峰响应与费米面嵌套矢量一致，具有垂直于q的易磁化轴。这与在许多稀稀土Y合金中发现的{ \it螺旋}反铁磁序一致。相反，对均匀磁场的响应的易磁化轴沿着c轴。讨论了Gd-Y合金及其它稀土材料中传导电子在磁矩倾斜中的作用。
We employ a descriptor based machine-learning approach to assess the effect of chemical alloying on formation-enthalpy of rare-earth intermetallics. Application of machine-learning approaches in rare-earth intermetallic design have been sparse due to limited availability of reliable datasets. In this work, we developed an `in-house' rare-earth database with more than 600$+$ compounds, each entry was populated with formation enthalpy and related atomic features using high-throughput density-functional theory (DFT). The SISSO (sure independence screening and sparsifying operator) based machine-l…
Although discovery in hydrogen induced electronic transition within perovskite family of rare-earth nickelate (ReNiO3) opens up a new paradigm in exploring both the new materials functionality and device applications, the existing research stays at ReNiO3 with light rare-earth compositions. To further extend the cognition towards heavier rare-earth, herein we demonstrate the hydrogen induced electronic transitions for quasi-single crystalline ReNiO3/LaAlO3 (001) heterostructures, covering a large variety of the rare-earth composition from Nd to Er. The hydrogen induced elevations in the resist…
Surface alloying is a straightforward route to control and modify the structure and electronic properties of surfaces. Here, We present a systematical study on the structural and electronic properties of three novel rare earth-based intermetallic compounds, namely ReAu2 (Re = Tb, Ho, and Er), on Au(111) via directly depositing rare-earth metals onto the hot Au(111) surface. Scanning tunneling microscopy/spectroscopy measurements reveal the very similar atomic structures and electronic properties, e.g. electronic states, and surface work functions, for all these intermetallic compound systems d…
Based on the electronic band structure obtained from first principles DFT calculations, the opticalspectra of yttrium and neodymium nickelates are computed. We show that the results are in fairagreement with available experimental data. We clarify the electronic transitions at the origin of thefirst two peaks, highlighting the important role of transitions from t2g states neglected in previousmodels. We discuss the evolution of the optical spectra from small to large rare-earth cations andrelate the changes to the electronic band structure.
In a bilayer of ferromagnetic and non-magnetic metal, spin pumping can be generated by a thermal gradient. The spin current generation depends on the spin mixing conductance of the interface and the magnetic properties of the ferromagnetic layer. Due to its low intrinsic damping, rare earth iron garnet is often used for the ferromagnetic layer in the spin Seebeck experiment. However, it is actually a ferrimagnetic with antiferromagnetically coupled magnetic lattices and the contribution of rare earth magnetic lattice of rare earth iron garnet on thermal spin pumping is not well understand. Her…
Here, we demonstrate two reliable routes for the fabrication of armchair-edge graphene nanoribbons (GNRs) on TbAu2/Au(111), belonging to a class of two-dimensional ferromagnetic rare earth-gold intermetallic compounds. On-surface synthesis directly on TbAu2 leads to the formation of GNRs, which are short and interconnected with each other. In contrast, the intercalation approach - on-surface synthesis of GNRs directly on Au(111) followed by rare earth intercalation - yields GNRs on TbAu2/Au(111), where both the ribbons and TbAu2 are of high quality comparable with those directly grown on clean…
