Orbital moments of 3d adatoms and Co nanostructures on Cu(0 0 1) surfaces

We use ab initio calculations to investigate spin and orbital moments of 3d transition-metal adatoms and Co nanostructures on Cu(0 0 1) surfaces. For Fe and Co adatoms on Cu(0 0 1) we predict extremely large orbital moments, comparable to the spin moments at these sites. For Mn and Cr adatoms the orbital moments are extremely small and can be neglected in face of their rather large spin moments. Ni adatoms on Cu(0 0 1) were found to be non-magnetic. Our investigations for adsorbed flat clusters of Co on Cu(0 0 1) address the persistence and extent of these large orbital moments in the clusters as a function of their size. We find that, the average orbital moment (M_orb) per Co atom is strongly correlated with the coordination number, decreasing drastically and monotonically as the average number of first Co neighbors around the sites in the cluster (N_Co) is increased.     

Chiral structures and tunable magnetic moments in 3d transition metal doped Pt₆ clusters

The structural, electronic, and magnetic properties of transition metal doped platinum clusters MPt 6 (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) are systematically studied by using the relativistic all-electron density functional theory with the generalized gradient approximation. Most of the doped clusters show larger binding energies than the pure Pt 7 cluster, which indicates that the doping of the transition metal atom can stabilize the pure platinum cluster. The results of the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps suggest that the doped clusters can have higher chemical activities than the pure Pt 7 cluster. The magnetism calculations demonstrate that the variation range of the magnetic moments of the MPt 6 clusters is from 0 μ B to 7 μ B , revealing that the MPt 6 clusters have potential utility in designing new spintronic nanomaterials with tunable magnetic properties.     

Chiral structures and tunable magnetic moments in 3d transition metal doped Pt6 clusters

The structural, electronic, and magnetic properties of transition metal doped platinum clusters MPt6 （M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn） are systematically studied by using the relativistic all-electron density functional theory with the generalized gradient approximation. Most of the doped clusters show larger binding energies than the pure Pt7 cluster, which indicates that the doping of the transition metal atom can stabilize the pure platinum cluster. The results of the highest occupied molecular orbital （HOMO） lowest unoccupied molecular orbital （LUMO） gaps suggest that the doped clusters can have higher chemical activities than the pure Pt7 cluster. The magnetism calculations demonstrate that the variation range of the magnetic moments of the MPt6 clusters is from 0 μB to 7 μB, revealing that the MPt6 clusters have potential utility in designing new spintronic nanomaterials with tunable magnetic properties.     

M@C_(20)H_(20)(M=Sc,V,Cr,Mn,Fe,Co,Ni)几何结构和电子性质的理论研究

采用密度泛函理论(DFT)中的广义梯度近似(GGA)方法对M@C_(20)H_(20)(M=Sc,V,Cr,Mn,Fe,Co,Ni)几何结构和电子性质进行了计算研究.几何结构优化发现,过渡金属原子M内掺到C_(20)H_(20)笼时,都稳定于碳笼中心.能隙和内掺能计算发现,M@C_(20)H_(20)的热力学稳定性随着M原子序数的增大而逐渐减弱,内掺M原子使得其动力学稳定性大幅度下降,但是其中Ni@C_(20)H_(20)结构仍然具有良好的热力学和动力学稳定性,其有望在实验中被成功合成出来.电子性质研究发现,随着M原子序数的逐渐增大,M原子对M@C_(20)H_(20)前线轨道的贡献也越来越大,M@C_(20)H_(20)(M=Sc,V,Cr,Mn,Fe,Co)都具有一定的磁矩,而Ni@C_(20)H_(20)为闭壳层结构,磁矩为零.     

Metastability of free cobalt and iron clusters: a possible precursor to bulk ferromagnetism

Homonuclear cobalt and iron clusters Co(N) and Fe(N) measured in a cryogenic molecular beam exist in two states with distinct magnetic moments (μ), polarizabilities, and ionization potentials, indicating distinct valences. The μ is approximately quantized: μ(N)～2Nμ(B) in the ground states and μ(N)(*)～Nμ(B) in the excited states for Co; μ(N)～3Nμ(B) and μ(N)(*)～Nμ(B) for Fe. At a large size, the average μ of the two states converges to the bulk value with diminishing ionization potential differences. The experiments suggest localized ferromagnetism in the two states and that itinerant ferromagnetism emerges from their superposition.     

密度泛函理论对CoBen(n=1—12)团簇结构和性质的研究

采用密度泛函理论中的广义梯度近似(GGA)对CoBe_n(n=1—12)团簇的几何构型进行优化，并对能量、频率和磁性进行了计算，同时考虑了电子的自旋多重度.得到了CoBe_n(n=1—12)团簇最低能量结构的自旋多重度是2和4.在CoBe_n(n=1—12)团簇中，Co原子的磁矩出现了奇偶振荡，当n=6时，Co原子的4s，3d和Be原子的2s，2p较强杂化、Co-Be键长的减小以及对称性的降低导致Co原子的磁矩最小.通过对CoBe_n(n=1—12)团簇电子性质的分析，得出了掺杂可以增强团簇稳定性和有利于增加合金化学活性的结论.n=5，10是团簇的幻数. 关键词： n团簇')" href="#">CoBe_n团簇 自旋多重度 磁矩 电子性质     

Co doping effects on structural, electronic and magnetic properties in Mn2VGa

The electronic structure and magnetic properties of Co-doped Heusler alloys (Mn_1−xCo_x)₂ VGa (x=0.0, 0.25, 0.5, 0.75, 1.0) have been studied by first-principles calculations. The results show that the lattice constants decrease with increasing Co content except x=1.0. The spin polarization for x=0.5 is only 34%, much lower than the other concentrations. The compounds of x=0.0, 0.25 show nearly half-metallicity because the Fermi level slightly touches the valence bands. And the compounds of x=0.75, 1.0 exhibit the half-metallic character with 100% spin polarization. It is found the local moments of Mn(Co) basically show a linear increasing trend while the moments of V show a linear decreasing trend with increasing doping concentration. However, the local moments for x=0.5 quite depart from the linear trend. The majority-spin component at the Fermi level increases while the minority-spin component at the Fermi level decreases with the substitution of Co atoms for Mn atoms when x≤0.75. For x≥0.75, the majority-spin component remains more or less the same and the gap in the minority DOS increases with Co doping. The majority spin states are shifted to valence bands and the majority spin states around E_F increase due to a leakage of charge from the unoccupied spin-up states to the occupied majority states with increasing Co content.     

Structural, electronic and magnetic properties of Mn, Co, Ni in Gen for (n=1-13)

The structural, electronic and magnetic properties of TMGe_n (TM=Mn, Co, Ni; n=1-13) have been investigated using spin polarized density functional theory. The transition metal (TM) atom prefers to occupy surface positions for n<9 and endohedral positions for n≥9. The critical size of the cluster to form endohedral complexes is at n=9, 10 and 11 for Mn, Co and Ni respectively. The binding energy of TMGe_n clusters increases with increase in cluster size. The Ni doped Ge_n clusters have shown higher stability as compared to Mn and Co doped Ge_n clusters. The HOMO-LUMO gap for spin up and down electronic states of Ge_n clusters is found to change significantly on TM doping. The magnetic moment in TMGe_n is introduced due to the presence of TM. The magnetic moment is mainly localized at the TM site and neighbouring Ge atoms. The magnetic moment is quenched in NiGe_n clusters for all n except for n=2, 4 and 8.     

Magnetic moments and adiabatic magnetization of free cobalt clusters

Magnetizations and magnetic moments of free cobalt clusters Co(N) (12 < N < 200) in a cryogenic (25 K < or = T < or = 100 K) molecular beam were determined from Stern-Gerlach deflections. All clusters preferentially deflect in the direction of the increasing field and the average magnetization resembles the Langevin function for all cluster sizes even at low temperatures. We demonstrate in the avoided crossing model that the average magnetization may result from adiabatic processes of rotating and vibrating clusters in the magnetic field and that spin relaxation is not involved. This resolves a long-standing problem in the interpretation of cluster beam deflection experiments with implications for nanomagnetic systems in general.     

Giant magnetic moments of nitrogen-doped Mn clusters and their relevance to ferromagnetism in Mn-doped GaN

Calculations based on density-functional theory show that the stability and magnetic properties of small Mn clusters can be fundamentally altered by the presence of nitrogen. Not only are their binding energies substantially enhanced, but also the coupling between the magnetic moments at Mn sites remains ferromagnetic irrespective of their size or shape. In addition, these nitrogen-doped Mn clusters carry giant magnetic moments ranging from 4mu(B) in MnN to 22mu(B) in Mn5N. It is suggested that the giant magnetic moments of MnxN clusters may play a key role in the ferromagnetism of Mn-doped GaN which exhibit a wide range (10-940 K) of Curie temperatures.     

Experimental observation of superparamagnetism in manganese clusters

A molecular beam of manganese clusters, Mn (n) (n = 11-99), produced at 68 K is deflected toward high field by a gradient field magnet. These results indicate that Mn (n) clusters in this size range are superparamagnetic species whose intrinsic moments can be determined within the framework of the Langevin model of paramagnetism. Local minima in per-atom magnetic moments are observed for Mn (13) and Mn (19), suggestive of an icosahedral growth sequence for the smaller size range. For larger clusters, broad oscillations in the per-atom moments are observed, with a minimum near Mn (32-37) and a maximum around Mn (50-56).     

Mg12O12纳米线掺杂3过渡金属元素的第一性原理计算研究

基于密度泛函第一性原理计算,系统研究了Mg12O12笼状团簇组装一维纳米线及其掺杂3d族元素体系的几何结构与电子结构。结果表明：Mg12O12团簇组装一维纳米线为非磁性半导体,带隙值为3.16 eV;掺杂Sc和V后,体系由半导体转变为金属;掺杂Ti、Cr、Mn、Fe、Co、Ni、Cu后体系仍然保持半导体特性、但带隙值明显减小,而掺杂Zn时带隙值变化不大;掺杂V、Cr、Mn、Fe、Co、Ni、Cu后纳米线具有磁性。     

A giant enhancement of magnetic moment in a ternary three-shell icosahedral cluster: Fe@Mn12@Au20

ABSTRACT

The average magnetic moment per atom of Mn₁₃ cluster is expected to be enhanced by doping or coating with a shell. Several ternary core–shell icosahedral clusters TM@Mn₁₂@Au₂₀ were constructed by combining substituting the central Mn with VIII elements (Fe, Co, Ni, Ru, Rh, Pd and Pt) and coating with a icosahedral Au₂₀ shell, and systematically studied by using the first-principles density functional method. Compared to Mn₁₃, Fe@Mn₁₂@Au₂₀ cluster shows a giant enhancement on total magnetic moment (52?µ_B) which can be greatly attributed to the ferromagnetic coupling between spin moments of atoms. Coating with Au₂₀ shell enlarged the average distances of TM-Mn and Mn-Mn and is a useful way to change the magnetic coupling style. By analysis of density of states and electron localisation functional, we can conclude that the weak hybridisation between Fe and Mn in Fe@Mn₁₂@Au₂₀ is propitious to maintain their original direction of spin moments of atoms and then form ferromagnetic coupling.     

Density functional study of small cobalt-platinum nanoalloy clusters

The structural, energetic, electronic and magnetic properties of small bimetallic Co_nPt_m (n+m≤5) nanoalloy clusters are investigated by density functional theory within the generalized gradient approximation. A plausible candidate for the ground state isomer and the other possible local minima, binding energies, relative stabilities, magnetic moments, the highest occupied and the lowest unoccupied molecular orbital energy gaps have been calculated. It is found as a general trend that average binding energies of Co-Pt bimetallic clusters increase with Pt doping. Planar structures of pure Co clusters become 3D with the addition of Pt atoms. CoPt₂, Co₂Pt₂, Co₃Pt₂, and CoPt₄ nanoalloys are identified as the most stable species since they have higher second finite difference in energy than the others. Pt doping decreases the total spin magnetic moment gradually. A rule for the prediction of the total spin moments of small Co-Pt bimetallic clusters is derived.     

Supported fe nanoclusters: evolution of magnetic properties with cluster size

Using a density functional approach, we study structural and magnetic properties of small Fe(n) clusters (n相似文献   

Dopant dependent stability of Co n TM+ (TM = Ti,V, Cr,and Mn) clusters

In this paper, we present a photofragmentation study of mass-selected transition metal-doped cobalt cluster cations Co _n TM⁺  (n = 8–18, TM = Ti, V, Cr, and Mn). Time-of-flight spectra recorded after laser excitation of mass-selected clusters in the gas phase show that the evaporation of a cobalt atom is the most facile dissociation channel for clusters with TM = Ti and V, suggesting an enhanced stability of the doped clusters compared to the bare ones. In contrast, for Co _n TM⁺ with TM = Cr and Mn, the loss of the dopant atom is found to be the preferred dissociation channel. Co₁₃Cr⁺ is a notable exception and favors dissociation by loss of a neutral Co atom. It is implied that substituting Mn and Cr generally destabilizes the cobalt clusters with the exception of Co₁₂Cr⁺, which is relatively more stable than Co ₁₃ ⁺ . Additional measurements of V _n Co⁺ (n = 9–16) show that the loss of a Co atom is still the most facile dissociation channel, which is in agreement with the predicted stronger V?V bond compared to the V?Co one.     

DFT study on size-dependent geometries, stabilities, and electronic properties of AunM2 (M = Si, P; n = 1–8) clusters

The ab initio method based on density functional theory at the PW91PW91 level has been employed to systematically study the structures, stabilities, electronic, and magnetic properties of gold clusters with or without silicon/phosphorus doping. The optimized geometries show that the most stable isomers for Au _n Si₂ and Au _n P₂ (n = 1–8) clusters prefer a three-dimensional structure when n = 2 and n = 3 upwards, respectively, and they can be viewed as grown from the already observed Au _n−1M₂ (M = Si, P). The relative stabilities of calculated Au _n M₂ (M = Si, P) clusters have been analyzed through the atomic average binding energy, fragmentation energy, second-order difference of energy, and HOMO-LUMO gap. A pronounced odd-even alternative phenomenon indicates that the clusters with even-numbered valence electrons possess a higher stability than their neighboring ones. For both systems, natural population analysis reveals that electronic properties of dopant atoms in the corresponding configuration are mainly related to s and p states. We also investigated magnetic effects of clusters as a function of cluster size, however, their oscillatory magnetic moments were found to vary inversely to the fragmentation energy, second-order difference of energy, and HOMO-LUMO gap.     

The magnetoelectric properties of A- or B-site-doped PbVO3 films： A first-principles study

We employ first-principles calculations to study the magnetic and ferroelectric properties of PbVO3 with A （XA = Ca, Sr, Bi, Ba, and La） or B （XB = Ti, Cr, Mn, Fe, Co, Ni, and Cu） site dopants, with the aim of ascertaining a large ferroelectric polarization and a long magnetic order, or even a macro fen＇i/ferromagnetism, which is critical to their potential applications in magnetoelectronic devices. It is found that PbTXAVsO24 （XA =Ca, Sr, and Ba,） are inclined to maintain the spin glass and large ferroelectric polarization. The degenerated G- and C-antiferromagnetic （AFM） couplings in the ideal PbVO3 are broken up, accompanied by the loss of ferroelectric properties, when La or Bi is doped at the A site. In contrast, the above-mentioned 3d transition elements doped at the B site of PbVO3 could induce remnant magnetic moments and preserve the large ferroelectric polarization, except for Ni and Cu. The Fe or Cr at the B site clearly remove the degenerated G- and C-AFM coupling, but the nonmagnetic Ti cannot do so. For the Mn, Co, Ni, or Cu doped at the B sites, even the two-dimensional AFM ordering in PbVO3 is destabilized. The various doping effects are further discussed with inner strain and charge transfer.     

新型超导材料MgCNi3的电子结构与超导电性研究

用MS-Xα方法研究了非氧化物超导材料MgCNi₃的电子结构. 研究结果显示, 态密度分布曲线的主峰靠近Fermi面, 主要来自于Ni的d电子的贡献. 用T(T=Co，Mn，Cu)替代MgCNi₃中的部分Ni形成化合物MgCNi₂T，替代使Ni的价电子数减小, 价态发生变化, Fermi面处态密度N(E_F)减小. 计算结果表明：无论是电子掺杂（Cu）还是空穴掺杂（Co，Mn），MgCNi₃的超导电 关键词： 电子结构 态密度 超导电性     

Spin and orbital magnetic moments of free nanoparticles

The determination of spin and orbital magnetic moments from the free atom to the bulk phase is an intriguing challenge for nanoscience, in particular, since most magnetic recording materials are based on nanostructures. We present temperature-dependent x-ray magnetic circular dichroism measurements of free Co clusters (N=8-22) from which the intrinsic spin and orbital magnetic moments of noninteracting magnetic nanoparticles have been deduced. An exceptionally strong enhancement of the orbital moment is verified for free magnetic clusters which is 4-6 times larger than the bulk value. Our temperature-dependent measurements reveal that the spin orientation along the external magnetic field is nearly saturated at ~20 K and 7 T, while the orbital orientation is clearly not.