Direct observation of orbital magnetism in cubic solids

We present x-ray magnetic circular dichroism determinations of the orbital/spin magnetic moment ratios of dilute 3d-series impurities in Au (and Cu) host matrices. This is the first direct measurement of considerable orbital moments in cubic symmetry for a localized impurity in a bulk metal host. It is shown that the unquenching of orbital magnetism depends on a delicate balance of hybridization effects between the local impurity with the host and the filling of the 3d states of the impurity. The results are accompanied by ab initio calculations that support our experimental findings.     

Magnetic impurities in Cu and Ag

We report self-consistent calculations for the electronic and magnetic structure of 3d-impurities in Cu and Ag. Exchange and correlation effects between the electrons are treated in the local spin-density approximation, and the corresponding one-electron Schroedinger equation is solved by the Korringa-Kohn-Rostocker-Green's function method. Without adjustable parameters we obtain results for the local density of states and the magnetic moments of the impurities.     

Lattice size induced moment formation on isolated Fe atoms in nanocrystalline Nb

Measurements of the local susceptibility and 3d spin relaxation rate for single Fe impurities embedded in a nanocrystalline Nb host indicates the emergence of a local moment on Fe at and below a critical size of 11?nm. Our ab?initio electronic structure calculations show that the moment formation occurs due to Stoner enhancement arising from a size dependent lattice expansion and a consequent shift in the Fermi level. We also show that a size-induced positive host spin polarization of the Nb-4d band electrons strongly influences the fluctuation rate of the Fe moment.     

Theory of localized magnetic moments in metals I finite cluster approach

The origin of localized magnetic moments formation in metals is investigated theoretically using a self-consistent local spin density molecular cluster approach. Clusters with up to 55 atoms are employed to describe isolated impurity local moment behavior in the cases of Fe$\text{Ag}$ and Fe$\text{Pd}$. Densities of states and spin magnetic moments were determined and compared with results of spectroscopic (notably photoemission) and magnetization measurements, respectively. In the case of a noble metal host, the spin magnetization density is found to be highly localized around the Fe site; the iron moment is ≈ 3.9μ_B and the polarization of the host Ag atoms is small. In the case of a transition metal host, the iron moment is ≈ 3.2 μ_B but here the strong hybridization of the Fe-3d and Pd-4d states results in a large induced magnetic moment in the host PD metal — in essential agreement with experiment for this giant moment system.     

Structural, electronic and magnetic properties of the 3d transition metal-doped GaN nanotubes

We have performed first-principles calculations on the structural, electronic and magnetic properties of seven different 3d transition-metal (TM) impurity (V, Cr, Mn, Fe, Co, Ni and Cu) doped armchair (5,0) and zigzag (8,0) gallium nitride nanotubes (GaNNTs). The results show that there is distortion around 3d TM impurities with respect to the pristine GaNNTs for 3d TM-doped (5,5) and (8,0) GaNNTs. The change of total magnetic moment follows Hund’s rule for 3d TM-doped (5,5) and (8,0) GaNNTs, respectively. The total density of states (DOS) indicates that Cr-, Mn-, Fe- and Ni-doped (5,5) GaNNTs as well as Cr-, Mn-, Ni- and Cu-doped (8,0) GaNNTs are all half-metals with 100% spin polarization. The study suggests that such TM-doped nanotubes may be useful in spintronics and nanomagnets.     

Impurities in noncubic crystals: stabilization mechanisms for Jahn-Teller ions in layered perovskites

Mechanisms responsible for the local geometry around Jahn-Teller impurities in K2NiF4 type lattices are shown to be different from those generating the warping in cubic crystals. The present density functional theory calculations reveal that the elastic anisotropy of the host lattice (visible for closed shell impurities) and the electric field created by the rest of lattice ions upon active electrons make it possible to have d(9) ions in an elongated geometry but with a A(1g) ground state. The puzzling difference between equilibrium geometries for Cu2+ and Ni+ in layered perovskites can reasonably be understood.     

Calculation of hyperfine interaction parameters in metals-friedel oscillations in dilute Fe and Cu alloys

We review some recent calculations on hyperfine interaction parameters in metals based on density functional theory in the local density approximation. We restrict ourselves to the calculation of Friedel oscillations of the charge and magnetization density in dilute Fe and Cu alloys. In particular, we estimate hyperfine fields, isomer shifts and electric field gradients for a few shells around the impurities. The calculations are performed using the KKR-Green's function method. Especially, we discuss which valence properties determine the hyperfine interaction parameters and what information about the electronic structure can be obtained from their measurement.     

Ab initio investigation of local magnetic structures around substitutional 3d transition metal impurities at cation sites in III-V and II-VI semiconductors

The local magnetic structures around substitutional 3d transition metal impurities at cation sites in zinc blende structures of III-V (GaN, GaAs) and II-VI (ZnTe) semiconductors are investigated by using a spin-polarized density functional theory. We find that Cr-, Co-, Cu-doped GaN, Cr-, Mn-doped GaAs and Cr-, Fe-, Ni-doped ZnTe are half metallic with 100% spin polarization. The magnetic moments due to these 3d transition metal (TM) ions are delocalized quite significantly on the surrounding ions of host semiconductors. These doped TM ions have long range interactions mediated through the induced magnetic moments in anions and cations of host semiconductors. For low impurity concentrations Mn in GaAs also has zero magnetic moment state due to Jahn-Teller structural distortions. Based upon half metallic character and delocalization of magnetic moments in the anions and cations of host semiconductors these above mentioned 3d TM-doped GaN, GaAs and ZnTe seem to be good candidates for spintronic applications.     

Origin of the giant magnetic moments of Fe impurities on and in Cs films

We have explored the origin of the observed giant magnetic moments ( approximately 7&mgr;(B)) of Fe impurities on the surface and in the bulk of Cs films, using the relativistic local-spin-density-approximation method. We have found that Fe impurities in Cs behave differently from those in noble metals or in Pd. Whereas the induced spin polarization of Cs atoms is negligible, the Fe ion itself is a source of the giant magnetic moment. The 3d electrons of Fe in Cs are localized as the 4f electrons in rare-earth ions so that the orbital magnetic moment becomes as large as the spin magnetic moment. The calculated total magnetic moment M = 6.43&mgr;(B) is close to the experimentally observed value.     

Strain field due to transition metal impurities in Ni and Pd

The strain field due to body centered substitutional transition metal impurities in Ni and Pd metals are investigated. The calculations are carried out in the discrete lattice model of the metal using Kanzaki lattice static method. The effective ion-ion interaction potential due to Wills and Harrison is used to evaluate dynamical matrix and the impurity-induced forces. The results for atomic displacements due to 3d, 4d and 5d impurities (Fe, Co, Cu, Nb, Mo, Pd, Pt and Au) in Ni and (Fe, Co, Cu, Ni, Nb, Mo, Pt and Au) impurities in Pd are given up to 25 NN’s of impurity and these are compared with the available experimental data. The maximum displacements of 4.6% and 3.8% of 1NN distance are found for NiNb and PdNb alloys respectively, while the minimum displacements of 0.63% and 0.23% of 1NN distance are found for NiFe and PdFe alloys respectively. Except for Cu, the atomic displacements are found to be proportional to the core radii and d state radius. The relaxation energies for 3d impurities are found less than those for 4d and 5d impurities in Ni and Pd metals. Therefore, 3d impurities may easily be solvable in these metals.     

Hyperfine Interactions and Magnetism of 3d Transition-Metal-Impurities in II–VI and III–V Compound-Based Diluted Magnetic Semiconductors

The electronic structure of II–VI and III–V compound-based diluted magnetic semiconductors is calculated based on the local density approximation (LDA) using the Korringa–Kohn–Rostoker method combined with the coherent potential approximation. The magnetism of 3d transition-metal-atom-doped ZnO, ZnS, ZnSe, ZnTe, GaN, GaAs is investigated from first-principles. It is suggested that the double exchange mechanism stabilizes the ferromagnetism in these DMSs. In order to obtain microscopic information on the electronic structure of transition-metal-impurities in semiconductors, the hyperfine field of respective impurities in each host material is calculated. It is found that the agreement with the experimental values is not good, probably because the LDA is not sufficient to describe the core states of transition metals. However, it is suggested that the hyperfine fields clearly reflect the local magnetic moments for 3d impurities. This revised version was published online in September 2006 with corrections to the Cover Date.     

3d过渡金属原子单层在Pd(001)表面磁性的第一性原理研究

用第一性原理基础上的超软赝势方法的总能计算，研究了3d过渡金属(Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn)在Pd(001)表面的单层p(1×1)和c(2×2)结构的表面磁性和总能. 所得结果表明：对于Sc, Ti, V和Cr只存在p(1×1)的铁磁性结构，而Mn只有c(2×2)的反铁磁结构存在. Fe, Co和Ni这三种元素上述两种结构都存在，但是总能上p(1×1)的铁磁结构要低些，因此是比较稳定的结构. 而Cu和Zn在该表面上的单层中不存在上述两种结构. 对于V的p(1×1)铁磁结构，计算得到的每个V原子磁矩为2.41μ_B，大于用全电子方法得到的0.51μ_B. 两种计算方法得到其他金属原子 (Cr，Mn，Fe，Co，Ni)的表面磁矩比较相近，都比孤立原子磁矩略小. 关键词： Pd(001)表面 过渡金属原子单层 表面磁性     

Effects of the 3d transition metal doping on the structural,electronic, and magnetic properties of BeO nanotubes

First-principles calculations have been performed on the structural, electronic, and magnetic properties of seven 3d transition-metal(TM) impurities(V, Cr, Mn, Fe, Co, Ni, and Cu) doped armchair(5,5) and zigzag(8,0) beryllium oxide nanotubes(BeONTs). The results show that there exists a structural distortion around the 3d TM impurities with respect to the pristine BeONTs. The magnetic moment increases for V- and Cr-doped BeONTs and reaches a maximum for Mn-doped BeONT, and then decreases for Fe-, Co-, Ni-, and Cu-doped BeONTs successively, consistent with the predicted trend of Hund’s rule to maximize the magnetic moments of the doped TM ions. However, the values of the magnetic moments are smaller than the predicted values of Hund’s rule due to the strong hybridization between the 2p orbitals of the near O and Be ions of BeONTs and the 3d orbitals of the TM ions. Furthermore, the V-, Co-, and Ni-doped(5,5) and(8,0) BeONTs with half-metal ferromagnetism and thus 100% spin polarization character are good candidates for spintronic applications.     

Impurity-induced local magnetism and density of states in the superconducting state of YBa2Cu3O7

17O NMR is used to probe the local influence of nonmagnetic Zn and magnetic Ni impurities in the superconducting state of optimally doped high TC YBa2Cu3O7. Zn and Ni induce a staggered paramagnetic polarization, similar to that evidenced above TC, with a typical extension xi=3 cell units for Zn and xi>or=3 for Ni. In addition, Zn is observed to induce a local density of states near the Fermi energy in its neighborhood, which also decays over about 3 cell units. Its magnitude decreases sharply with increasing temperature. This allows direct comparison with the STM observations done in BiSCCO.     

Magnetic properties of 3d transition metal monolayers on metal substrates

We report results of systematic calculations for magnetic properties of 3d transition metal monolayers on Pd(001) and Ag(001). We find large similarities to interactions of magnetic 3d impurities in the bulk. Therefore the overlayer results are supplemented with results for 3d dimers in Cu, Ag, and Pd. Differences between the two classes of systems are utilized to reveal the interaction within the overlayers and between overlayers and substrates. In virtually all cases we find both ferromagnetic and antiferromagnetic solutions, showing large magnetic moments and similar densities of states. From the trend of the calculations we conclude that V, Cr, and Mn overlayers favor the antiferromagnetic c(2×2) structure, while Ti, Fe, Co, and Ni prefer the ferromagnetic one.     

Dynamics of the local moment induced by nonmagnetic defects in cuprates

We present a study of the spin dynamics of magnetic defects induced by Li substitution of the plane Cu in the normal state of YBa2Cu3O6+x. The fluctuations of the coupled Cu magnetic moments in the vicinity of Li are probed by near-neighbor 89Y and 7Li NMR spin lattice relaxation. The data indicate that the magnetic perturbation fluctuates as a single entity with a correlation time tau which scales with the local static susceptibility. This behavior is reminiscent of the low T Kondo state of magnetic impurities in conventional metals. Surprisingly it extends well above the "Kondo" temperature for the underdoped pseudogapped case.     

Atomic displacements in bcc dilute alloys

We present here a systematic investigation of the atomic displacements in bcc transition metal (TM) dilute alloys. We have calculated the atomic displacements in bcc (V, Cr, Fe, Nb, Mo, Ta and W) transition metals (TMs) due to 3d, 4d and 5d TMs at the substitutional site using the Kanzaki lattice static method. Wills and Harrison interatomic potential is used to calculate the atomic force constants, the dynamical matrix and the impurity-induced forces. We have thoroughly investigated the atomic displacements using impurities from 3d, 4d and 5d series in the same host metal and the same impurity in different hosts. We have observed a systematic pattern in the atomic displacements for Cr-, Fe-, Nb-, Mo-, Ta-and W-based dilute alloys. The atomic displacements are found to increase with increase in the number of d electrons for all alloys considered except for V dilute alloys. The 3d impurities are found to be more easily dissolved in the 3d host metals than 4d or 5d TMs whereas 4d and 5d impurities show more solubility in 4d and 5d TMs. In general, the relaxation energy calculation suggests that impurities may be easily solvable in 5d TM hosts when compared to 3d or 4d TMs.      

Magnetic hyperfine fields of 5sp impurities in vacancy complexes in ferromagnetic metals

A survey is given of recent experimental results for the hyperfine interactions of 5sp impurities in vacancy complexes in ferromagnetic 3d host metals. Emphasis is put on changes of the impurity magnetic hyperfine fields in such complexes as compared to substitutional lattice sites. Systematic trends are presented, which are beginning to emerge from studies of Cd and Sn impurities in particular.     

Room-temperature ferromagnetism of Cu-doped ZnO films probed by soft X-ray magnetic circular dichroism

We report direct evidence of room-temperature ferromagnetic ordering in O-deficient ZnO:Cu films by using soft x-ray magnetic circular dichroism and x-ray absorption. Our measurements have revealed unambiguously two distinct features of Cu atoms associated with (i) magnetically ordered Cu ions present only in the oxygen-deficient samples and (ii) magnetically disordered regular Cu2+ ions present in all the samples. We find that a sufficient amount of both oxygen vacancies (V(O)) and Cu impurities is essential to the observed ferromagnetism, and a non-negligible portion of Cu impurities is uninvolved in the magnetic order. Based on first-principles calculations, we propose a microscopic "indirect double-exchange" model, in which alignments of localized large moments of Cu in the vicinity of the V(O) are mediated by the large-sized vacancy orbitals.     

Density functional theory description of the mechanism of ferromagnetism in nitrogen-doped SnO2

Based on first-principles calculations, we have studied the occurrence of spin polarization in the magnetic metal oxide SnO₂ doped with nonmagnetic nitrogen (N) impurities. It was found that the local magnetic moments are localized mainly on the N dopant, causing a total moment of 0.95μB per cell. The long-range magnetic coupling of N-doped SnO₂ may be attributed to a p-p coupling interaction between the N impurity and host valence states.