The electronic structure and the ferromagnetic intermolecular interactions in the crystal of TEMPO radicals

Based on the generalized gradient approximation, full potential linearized augmented plane wave (FP-LAPW) calculations have been performed to study the electronic band structure and the intermolecular ferromagnetic (FM) interactions for the two TEMPO radicals 4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-1-oxyl (1) and 4-(2-naphtylmethyleneamino)-2,2,6,6-tetramethylpiperidin-1-oxyl (2). The total and the partial density of states and the atomic spin magnetic moments are calculated and discussed. The calculation revealed that the two TEMPO radicals have the intermolecular FM interactions, and the spontaneous magnetic moment is 1.0 μ_B per molecule of each crystal, which is in good agreement with the experimental value. It is found that the unpaired electrons in these compounds are localized in a molecular orbital constituted primarily of π* (NO) orbital, and the main contribution of the spin magnetic moment comes from the NO-free radical. The origin of FM is also studied in detail.     

Electronic and Magnetic Properties of the p-NPNN

In this paper, we study the electronic band structure and the ferromagnetic properties of the organic radicalp-NPNN by employing density-functional theory with generalized gradient approximation (GGA) and local-spin densityapproximation (LSDA). The density of states, the total energy, and the spin magnetic moment are calculated. Thecalculations reveal that the δ-phase of p-NPNN has a stable ferromagnetic ground state. It is found that an unpairedelectron in this compound is localized in a single occupied molecular orbital (SOMO) constituted primarily of π* (NO)orbitals, and the main contribution of the spin magnetic moment comes from the π* (NO) orbitals. By comparison, wefind that the GGA is more suitable to describe free radical systems than LSDA.     

Electronic and Magnetic Properties of the p-NPNN

In this paper, we study the electronic band structure and the ferromagnetic properties of the organic radical p-NPNN by employing density-functional theory with generalized gradient approximation (GGA ) and local-spin density approximation (LSDA). The density of states, the total energy, and the spin magnetic moment are calculated. The calculations reveal that the δ-phase of p-NPNN has a stable ferromagnetic ground state. It is found that an unpaired electron in this compound is localized in a single occupied molecular orbital (SOMO) constituted primarily of π^* (NO) orbitals, and the main contribution of the spin magnetic moment comes from the π^* (NO) orbitals. By comparison, we find that the GGA is more suitable to describe free radical systems than LSDA.     

First-principles study on the electronic structure and the ferromagnetic properties of the cyano-bridged bimetallic compound Mn2(H2O)5Mo(CN)7·4H2O (α phase)

First-principles calculations have been performed to study the electronic structure and the ferromagnetic properties of the cyano-bridged bimetallic compound Mn₂(H₂O)₅Mo(CN)₇·4H₂O (α phase).The calculations were based on density-functional theory and the full potential linearized augmented plane wave method (FP-LAPW). The calculated total energies revealed that the compound has a stable ferromagnetic (FM) ground state, which is in agreement with the experiments. The electronic structure of the compound has a half-metallic behavior. The calculated magnetic moment per molecule is about 15.000 μ_B, the magnetic moment are mainly from Mo and Mn atoms with d electronic configuration. It is also found that there exists ferromagnetic interaction between low-spin Mo²⁺ and high-spin Mn³⁺ ions through the Mo-C-N-Mn linear linkages.     

The electronic structure and the ferromagnetic intermolecular interactions in the crystal of a diphenyl nitroxide derivative

Based on the generalized gradient approximation, full potential linearized augmented plane-wave calculations have been performed to study the electronic band structure and the ferromagnetic (FM) interactions of the 9,9-dipropyl-9,10-dihydroacridin-10-yloxyl (DPAO) organic radical. The total and partial density of states and the atomic spin magnetic moments are calculated and discussed. It is found that the unpaired electrons in this radical are localized in a molecular orbital constituted primarily of the π* (NO) orbital, and the main contribution of the spin magnetic moment comes from the NO free radical, with little contributions from other C atoms. The origin of FM interactions is also studied in detail.     

The ferromagnetic and half-metallic properties of the layered organic–inorganic hybrid Fe[CH3(CH2)2PO3(H2O)]

The density-functional theory (DFT) within the full potential linearized augmented plane wave (FPLAPW) method was applied to study the layered organic–inorganic hybrid Fe[CH₃(CH₂)₂PO₃(H₂O)]. The relative stability of the ground state, the electronic band structure, the magnetic and the conducting properties were investigated. The calculations reveal that the compound has a stable ferromagnetic ground state and the spin magnetic moment per molecule is about 4.0 μ_B, which is mainly from Fe(II) ion. By analysis of the band structure, we find that the compound has half-metallic properties.     

The first principle study on the electronic structure and spin ordering of the rare earth palladium sulfide, EuPd3S4

We have performed relativistic first-principles full-potential linearized augmented plane wave (FLAPW) calculation for rare earth palladium sulfide EuPd₃S₄ in the ferromagnetic and antiferromagnetic states. The density of 4f electrons of Eu is taken from a local-spin-density approximation self-interaction correction (LSDA-SIC) atomic calculation. EuPd₃S₄ is found to exhibit antiferromagnetic ordering in its ground state. The charge, orbital, magnetic moment and spin ordering are explained with the electronic structure, the orbital-projected density of states and the total energy study. EuPd₃S₄ is found to be stable in the body-centered Type-I antiferromagnetic state, in agreement with experimental results. Different Eu states are found in antiferromagnetic ordering. The magnetic moments of different states obtained through spin-polarized calculation are also in good agreement with experimental results. The phenomena observed are explained by the orbital hybridization of Eu and Pd ions as compared with the free ions.     

Magnetic properties,electronic structure,and optical properties of the filled skutterudite BaFe4Sb12

The magnetic properties, electronic structure, and optical properties of the filled skutterudite BaFe₄Sb₁₂ are calculated by the first-principles full-potential linearized augmented plane wave (FPLAPW) plus local orbital method. It is found that the local spin density approximation (LSDA) method appears more accurate than the generalized gradient approximation (GGA) method in calculating the electronic structures and optical properties of this compound. Furthermore, our calculated lattice constant and spin magnetic moments with the LSDA method are in overall better agreement with experiment. In contrast with recent experiment, our calculations are in good agreement with experimental reflectivity spectra and optical conductivity spectrum.     

First-principles study on the metallic antiferromagnet Co[PhPO3]·H2O

The electronic structure and the magnetic properties of transition metal phosphonate Co(PhPO₃)·H₂O have been studied by first-principles within the density-functional theory (DFT) and the full potential linearized augmented plane wave (FP-LAPW) method. The total energy, the total magnetic moment, the atomic spin magnetic moments and the density of states(DOS) of Co(PhPO₃)·H₂O were all calculated. The calculations reveal that the title compound is a metallic antiferromagnet and has a metallic ferromagnetic metastable state, which are in good agreement with the experiment. The spin magnetic moment of Co(PhPO₃)·H₂O is about 4.93 _μB${\mu }_{\mathrm{B}}$ per molecule, and it is mainly assembled at the cobalt atom, at the same time, with a little contribution from the P, O1, O2, O3.     

Theoretical investigation on structural, magnetic and electronic properties of ferromagnetic GdN under pressure

The tight-binding linear muffin tin orbital (TB-LMTO) method within the local density approximation is used to calculate structural, electronic and magnetic properties of GdN under pressure. Both nonmagnetic (NM) and magnetic calculations are performed. The structural and magnetic stabilities are determined from the total energy calculations. The magnetic to ferromagnetic (FM) transition is not calculated. Magnetically, GdN is stable in the FM state, while its ambient structure is found to be stable in the NaCl-type (B₁) structure. We predict NaCl-type to CsCl-type structure phase transition in GdN at a pressure of 30.4 GPa. In a complete spin of FM GdN the electronic band picture of one spin shows metallic, while the other spin shows its semiconducting behavior, resulting in half-metallic behavior at both ambient and high pressures. We have, therefore, calculated electronic band structures, equilibrium lattice constants, cohesive energies, bulk moduli and magnetic moments for GdN in the B₁ and B₂ phases. The magnetic moment, equilibrium lattice parameter and bulk modulus is calculated to be 6.99 μ_B, 4.935 Å and 192.13 GPa, respectively, which are in good agreement with the experimental results.     

Schottky-like anomaly in the low-temperature specific heat of single-crystal NdMnO3

The specific heat of single-crystal NdMnO₃ was investigated from 2 to 20 K under different magnetic fields up to 8 T. All the specific heat data show a Schottky-like anomaly, which becomes more indistinctive as increasing magnetic field. The experiment data were successfully fitted by taking into account factors such as crystal-field splitting, the two-level Schottky anomaly, the lattice vibration, and type-A antiferromagnetic (A-AF) spin waves. It was found that the splitting of the ground state doublet of Nd³⁺ ion increases linearly with magnetic field. The above phenomena can be interpreted in terms of the model of unchanged effective molecular field at Nd³⁺ site caused by the ferromagnetic component of A-AF structure of Mn spins. This ferromagnetic component is likely caused by the GdFeO₃-type octahedron rotation. In addition, it was also found that the magnetic field increases the spin-wave stiffness coefficient, but reduces the Debye temperature.     

Magnetic structure of geometrically frustrated compound Co2Cl(OH)3 determined by proton NMR

The magnetic structure of a geometrically frustrated system Co₂Cl(OH)₃ is determined by comparing the observed proton NMR spectrum with numerical calculations based on various magnetic models. The best fit is obtained with a model that the magnetic moments of Co²⁺ ions in the triangular plane are parallel to the principal axis of local crystal field and those of Co²⁺ ions in the kagome lattice plane are randomly disordered in the a-b plane, which nearly bisects the angle between the principal axis of the local field and a line pointing towards the body center of the tetrahedron. The coexistence of the ferromagnetic order in the triangular plane and the random disorder in the kagome plane is consistent with the results of measurements by Zheng et al. However, the magnetic moments of Co²⁺ ions are not directed towards the body center of the tetrahedron as characteristic in the “spin ice” magnetic structure. Furthermore, the Co²⁺ ions in the triangular plane have a smaller magnitude of magnetic moment than those in the kagome plane. Thus, our result suggests that the transition metal compound Co₂Cl(OH)₃ is different from the “spin ice” in magnetic structure, although it is similar to rare-earth pyrochlores in crystal structure.     

Electronic and magnetic properties of basic nanosystems of early 3d transition metals (Sc,Ti, V,Cr, and Mn)

This detailed and systematic theoretical study on the behavior of basic low dimensional (one- and two-dimensional) systems of early 3d transition metals should serve as a guideline to experimentalists as well as to theoreticians. We find that, lowering of dimensionality is favorable for emergence of magnetic ordering in all the systems studied, except Ti monolayers (MLs). For Ti MLs, both nonmagnetic and ferromagnetic states are degenerate within the numerical limits. For such a case, the interactions with substrate would play a decisive role in the magnetic ordering of the atoms in the ML. The total energy calculations show that the nonmagnetic and ferromagnetic states are almost degenerate for Cr and V MLs too; however, anti-ferromagnetic ordering is favored in these. The ferromagnetic ordering in Sc linear chains and anti-ferromagnetic ordering in MLs of Mn and Cr are found to be favored by a relatively larger margin showing good stability. Some low dimensional systems, showing electrons with only one kind of spin available at Fermi energy, may be suitable for spintronics related applications. The linear chains of Cr and Mn, and MLs of Sc are likely to form stable magnetic nanosystems as these exhibit almost saturated magnetic moment per atom around the equilibrium separation. The magnetic moment strengthens considerably as one goes from two- to one-dimension. Our results are supported qualitatively by available experimental results and offer a good insight into these nanosystems.     

Magnetic properties of the charge ordered Nd0.75Na0.25MnO3

Nd_0.75Na_0.25MnO₃ polycrystalline ceramic is prepared via sol-gel process and its magnetic properties and electron spin resonance (ESR) spectra have been investigated experimentally. As the compound is cooled from room temperature, a charge-ordered state first develops below 170 K. A high magnetic field melts the charge ordered state and stabilizes a ferromagnetic (FM) state below 170 K. A field induced transition, analogous to a spin flip transition, is observed between 40 and 170 K. The critical temperature for spin flip increases with increasing temperature. Below 130 K, the compound tends to be intrinsically inhomogeneous, i.e. FM clusters and paramagnetic domains coexist in this system at least, which is confirmed by ESR measurements. When the external magnetic field is zero, long range FM interaction is not developed in this system; however, a tendency of re-entrant FM transition is observed in this compound.     

Improving exchange-coupling field in the same thickness of pinned magnetic layer

A conventional Ta/NiFe/Cu/NiFe/FeMn spin valve was prepared to investigate the exchange bias properties with the variations of deposition field. By enhancing the deposition magnetic fields from 50 to 650 Oe, increase of exchange bias fields at a given thickness of the pinned NiFe layer has been found in the spin valves. In this paper, we show that this increase is due to the change of magnetic moment distribution at the ferromagnetic and antiferromagnetic interface by comparison of measured results with the interfacial uncompensated model. Therefore, by enhancing deposition magnetic fields, a large exchange-coupling field can be achieved in relatively thicker magnetic films for application.     

The electronic structure and magnetic properties of metallic antiferromagnetic Co[(CH3PO3)(H2O)] studied by first-principles calculations

The electronic structure, the metallic and magnetic properties of metal phosphonate Co[(CH₃PO₃)(H₂O)] have been studied by first-principles calculations, which were based on the density-functional theory (DFT) and the full potential linearized augmented plane wave (FPLAPW) method. The total energy, the spin magnetic moments and the density of the states (DOS) were all calculated. The calculations reveal that the compound Co[(CH₃PO₃)(H₂O)] has a stable metallic antiferromagnetic (AFM) ground state and a half-metallic ferromagnetic (FM) metastable state. Based on the spin distribution obtained from calculations, it is found that the spin magnetic moment of the compound is mainly from the Co²⁺, with some small contributions from the oxygen, carbon and phosphorus atoms, and the spin magnetic moment per molecule is 5.000μ_B, which is in good agreement with the experimental results.     

Spin injection-driven switching in a magnetic junction

We investigate a perpendicular electric current passing through a “ferromagnetic nanojunction”, that is through some layered nanosized structure of spin-valve type, containing two ferromagnetic metallic layers. Spacer may be used between the metallic layers to prevent the rotation of the moving spin phases. Such an arrangement is typical for spin valves: one of the metallic layers has strongly pinned magnetic lattice and the other one has free magnetic lattice and free mobile spins. Further the conditions are derived to provide a very high nonequilibrium spin injection level. It appears that the so-called spin resistances of the constitutive layers should be in definite relations to each other. These relations lead to the situation where the spin injection becomes dominant and significantly suppresses the “ordinary” spin-transfer torque. As a result, the threshold current becomes lowered down to 2-3 and even more orders of magnitude.     

化合物SmCo5的电子结构、自旋和轨道磁矩及其交换作用分析

用自旋极化的MS-Xα方法研究了稀土-过渡族化合物SmCo5₅的电子态密度、自 旋能级劈裂及原子磁矩.研究结果显示，由于化合物中Sm-Co间的轨道杂化效应，使Sm原子原来的5d00空轨道上占据了少量5d电子.由于Co(3d)-Sm(5d)电子间的直接交换作用，导致了Sm-Co间的磁性交换耦合，这是化合物中形成Sm-Co铁磁性长程序的一个重要原因.在SmCo5_{5化合物中存在6个能级呈现负交换耦合，导致了SmCo55化 关键词： 电子结构 自旋极化 原子磁矩 交换耦合}     

Ab initio study of magnetic property of BEST2 [Fe(CN)5NO] charge-transfer salt

By means of ab initio method of the full potential linearized augmented-plane-wave, electronic band structure and its magnetic property for a charge transfer compound of bis (ethylenediselena)-tetrathiafulvalene(BEST) with [Fe(CN)₅NO] anions are investigated for the first time, where the exchange-correlation effects of electrons are accounted in the generalized gradient approximation. The spin density of states and the magnetic moment are analyzed in detail. It is found that there exists a new antiferromagnetic coupling in the organic donors because of alternating spin population in the organic donors. Besides the localized 3d electrons of Fe in [Fe(CN)₅NO] anion, the ligand nitric oxide and the cyanogen radical play important roles in the magnetic properties of the system. Our results are in good agreement with the experimental observations.     

Observation of higher magnetization on the substitution of Al for Co in La2MnCoO6

Upon substitution of non-magnetic Al³⁺ for diamagnetic, low-spin, Co³⁺ in ferromagnetic La₂MnCoO₆, the ferromagnetic moment, measured at 82 K and 15 kOe, is found to increase initially with Al content and then decreases, though the magnetic transition temperature decreases continuously on increasing x in La₂MnCo_1−xAl_xO₆.