Stability and Growth Modes of Ni--C Clusters: A Study based on All-Electron Density Function Theory

Growth modes of the free-standing NiCN （N ≤ 8） and Ni2CN （N ≤ 8） dusters are investigated by the allelectron density functional theory. The results reveal that there are two competing modes for the growth of these clusters： the linear chain and the ring structure without transannular bonds. The lowest-energy geometries of NiCN （N ≤ 8） are the linear chains with the Ni atom at one end, except for NiC2 and NiCT. The Ni2CN （N ≤ 8） clusters all prefer to the linear chains with the two Ni atoms at the two ends. Miilliken population analysis indicates that the total spin of the lowest-energy cluster show significant odd-even alternation. The NiMCN （M = 1,2） clusters with the even N are one and those with the odd-N are zero.     

Room-Temperature Ferromagnetism in Zn1-xMnxO Thin Films Deposited by Pulsed Laser Deposition

Zn1-xMnxO （x = O.Olq3.1） thin films with a Curie temperature above 300K are deposited on Al2O3 （0001） substrates by pulsed laser deposition. X-ray diffraction （XRD）, ultraviolet （UV）-visible transmission and Raman spectroscopy are employed to characterize the microstructural properties of these films. Room temperature ferromagnetism is observed by superconducting quantum interference device （SQUID）. The results indicate that Mn doping introduces the incorporation of Mn^2＋ ions into the ZnO host matrix and the insertion of Mn^2＋ ions increases the lattice defects, which is correlated with the ferromagnetism of the obtained films. The doping concentration is also proven to be a crucial factor for obtaining highly ferromagnetic Zn1-xMnxO films.     

Tailor-made electronic and magnetic properties in one-dimensional pure and Y-substituted Ca3Co2O6

Full-potential density-functional calculations show that the electronic structure of one-dimensional ferrimagnetic Ca3Co2O6 varies from metal to half metal to insulator as its magnetic ordering changes from the ferrimagnetic through the ferromagnetic to the paramagnetic state. The present Letter is the first to establish the occurrence of half metallicity in one-dimensional oxides. Moreover, the electronic and magnetic properties of this material can be tuned by substitution of Y for Ca, as shown by our detailed study on Ca(3-x)YxCo2O6 (x = 0, 0.3, 0.75, and 1). The Co ions are in two different valence states [Co4+ (low-spin) and Co2+ (high-spin)], and hence the occurrence of charge ordering in addition to spin ordering is established. For specific Y concentrations we predict a rarely seen combination of ferromagnetic and insulating behavior.     

Cohesive properties of mercury clusters in the ground and excited states

Optimized structures and cohesive energies of small mercury clusters (Hg_N; N = 3–7, 13, 19) are calculated with the spin-orbit diatomics-in-molecules method. The theory takes into account the effect of s-p mixing which tends to enhance the binding energies in the ground state. It is shown that excimer clusters have significantly short optimum bond lengths and their atomic geometries differ considerably from those in the ground state. Excitation energy gap depends sensitively on both cluster size and nearest-neighbor separation. Numerical results are compared with other theories and experiments.     

Dilute ferrimagnetism of ilmenites Mn<Subscript>3</Subscript>FeTiSbO<Subscript>9</Subscript> and Mn<Subscript>4</Subscript>FeTi<Subscript>2</Subscript>SbO<Subscript>12</Subscript>

Metastable solid solutions (SS) Mn₃FeTiSbO₉ and Mn₄FeTi₂SbO₁₂ with the ilmenite structure (space group R\(\bar 3\)) have been prepared by quenching at normal conditions. The compositions of the compounds have been justified using EDX spectroscopy and X-ray diffraction. The magnetic properties of SSs have been analyzed by comparison with ferrimagnetic ilmenite Mn₂FeSbO₆ (T_N = 269 K) as a natural mineral and ceramics obtained at high pressure and high temperature. The solid solutions have been characterized as dilute magnetic systems formed as a result of substitution of nonmagnetic cations Ti⁴⁺ for a part of Fe³⁺ and Sb⁵⁺ cations. Mn₃FeTiSbO₉ is considered as a ferromagnetic with T_N = 171 K and Mn₄FeTi₂SbO₁₂ as a magnetic with the concentration of magnetic clusters below the percolation threshold.     

Relations of electronic energies and magnetic moments of tetra-3d metal (Mn, Fe, Co and Ni) nitrides calculated using a plane-wave basis method

Geometrical optimization of tetra-3d metal nitrides (Mn₄N, Fe₄N, Co₄N, and Ni₄N) has been performed and the relations of their energies (E) and their total magnetic moments (M) are obtained by plane-wave-basis density-functional calculations without any assumption of specific spin arrangement. The E vs. M relations obtained for Fe₄N and Mn₄N have a bimodal character. The ground state of Fe₄N is a high-spin state, which would correspond to the ferromagnetic character, while that of Mn₄N is a low-spin state, which would correspond to the observed ferrimagnetic character. Lattice constants and total magnetic moments of these tetra-3d metal nitrides are almost accurately predicted. From the spin-polarized densities of states curves, Co₄N would have the largest spin polarization ratio of 0.88, which suggests Co₄N can be a candidate material for ferromagnetic electrodes for spin-injection.     

An Effective Method of Producing Small Neutral Carbon Clusters

An effective method of producing small neutral carbon dusters Cn （n = 1-6） is described. The small carbon dusters （positive or negative charge or neutral） are formed by plasma which are produced by a high power 532nm pulse laser ablating the surface of the metal Mn rod to react with small hydrocarbons supplied by a pulse valve, then the neutral carbon clusters are extracted and photo-ionized by another laser （266nm or 355nm） in the ionization region of a linear time-of-flight mass spectrometer. The distributions of the initial neutral carbon dusters are analysed with the ionic species appeared in mass spectra. It is observed that the yield of small carbon dusters with the present method is about 10 times than that of the traditional widely used technology of laser vaporization of graphite.     

Magnetic properties and magnetoresistance effect of Y1-xGdxMn6Sn6 (x=0－1) compounds

The magnetic properties and magnetoresistance effect of Y_1-xGd_xMn₆Sn₆ (x=0－1) compounds have been investigated by magnetization and resistivity measurements in the applied field range (0－5 T). Compounds with x=0.4－1 display ferrimagnetic behaviours in the whole magnetic ordering temperature range, while compounds with x=0－0.2 display a field-induced metamagnetic transition, and the threshold fields decrease with increasing Gd content. The compounds with x=0.1－0.2 undergo an antiferromagnetic to ferromagnetic transition with increasing temperature. The cell-parameter a and c and cell-volume V of compounds (x=0－1) increase with increasing Gd content. It was found that the saturation magnetization M_s of the compounds (x=0.4－1) decreases, while the ordering points of the compounds (x=0－1)increase with increasing Gd content. A large MR effect was observed in the compound with x=0.2, and the maximum absolute value of MR at 5 K under 3 T is close to 19.3%.     

Substitution of manganese by trivalent and tetravalent elements in the CMR perovskites Pr1-x(Ca,Sr)xMnO3

The substitution of trivalent (M=In, Ga) and tetravalent elements (M=Sn, Ti) for Mn(III) and Mn(IV) respectively has been studied in the colossal magnetoresistant (CMR) perovskites Pr_0.7Ca_0.2Sr_0.1MnO₃ (type I) and Pr_0.5Sr_0.5MnO₃ (type II). For the former compound, whatever the element, the temperature transition (T_max or T_C) separating the ferromagnetic metallic (FM) state and the paramagnetic semiconductinc (PSC) state decreases dramatically when the substituted element content is increased, the saturated magnetic moment at low temperature being slightly decreased. For these type I perovskites the maximum magnetoresistance is achieved for Pr_0.7Ca_0.2Sr_0.1Mn_0.99Ga_0.01O₃, reaching a resistance ratio of 600 at 127rK against 275 at 151rK for the pristine sample. These results show that by decreasing or increasing the hole concentration via M(IV) or M(III) substitutions on the manganese site the Curie temperature T_C is always decreased. In contrast to the type I perovskites, two different effects are evidenced for the Pr_0.5Sr_0.5Mn_1-xM_xO₃ substituted type II phases depending on the M valence. On one hand for M=Ga, In when x increases the antiferromagnetic semiconducting (AFSC) state and the PSC state are favoured at the expense of ferromagnetism. On the other hand for M=Sn, Ti the low temperature AFSC state tends to disappear and for x>0.04 only a FM to PSC transition still exits similarly to that observed in type I perovskites. Correspondingly the magnetization versus temperature curves evolve from the bell shape curve typical of the charge ordering state to that of a ferromagnetic compound. The effect of valence and d⁰, d¹⁰ electronic configurations in both type I an II CMR perovskites is discussed.     

The magnetic structure of M-type hexaferrites

A symmetry analysis is presented of the possible types of magnetic ordering in hexagonal ferrimagnets having an (M type) magnetoplumbite structure. In the analysis the transition channel to a magnetically ordered state according to the k=0 star is considered. It is shown that the only general commuting representation for all regular point systems in such compounds is the unitary representation τ₁ corresponding to ferromagnetic ordering of the magnetic moments in sublattices. Antiferromagnetic exchange between ions of different sublattices leads to a collinear ferrimagnetic structure.     

Stability and fragmentation of multiply ionized clusters

The stability of neutral, singly and multiply ionized silicon clusters, (N = 2-7, M = 0, , , ), has been investigated using an ab initio density functional method. We show that the fragmentation effect significantly affects the structure of mass-spectra of multiply ionized silicon clusters. For clusters, the clusters with a large fragmentation energy are found to correspond to the high peaks at N = 4 and 6 in mass-spectra. For clusters, a peak at N = 5 in mass-spectra has been predicted to be especially high. Received: 9 June 1997 / Revised: 8 January 1998 / Accepted: 25 February 1998     

Accumulating evidence for the two-step magnetic ordering in the borocarbides DyNi2B2C and DyCo2B2C

Accumulating evidence for a two-step magnetic ordering in the borocarbide DyNi₂B₂C is summarized, including earlier overlooked evidence for the initial magnetic transition and a recent magnetization study of polycrystalline samples. The two-step ordering involves initial two-dimensional ferromagnetic ordering in the DyC (basal) planes at T_N (=16.3 K), gradual build-up of the three-dimensional (3D) alternate stacking of ferromagnetic planes, and a final 3D ordering in the AF–I-related structure at a lower temperature T_o (=10.4 K), depicting a first-order transition. Supporting evidence for the two-step magnetic ordering in DyNi₂B₂C comes from point-contact spectroscopy measurements in the normal state for DyNi₂B₂C–Ag contact, and from similar behaviour of PrNi₂B₂C and (Pr_0.91Dy_0.09)Ni₂B₂C. In the isostructural borocarbide DyCo₂B₂C the two magnetic transitions (at 7.8 and 2.6 K) deduced from the specific-heat measurements are also attributed to a two-step magnetic ordering.     

Unique Magnetic Moment and Electronic Properties for Fe（MgO）n（n=1-8） Clusters： First-Principles Calculations

The geometries and electronic properties of Fe（MgO）n are systematically investigated by the density functional theory. The results show that the doped Fe atom is prone to bond with the O atom, and Fe almost does not disturb the frame of （MgO）n. The second-order energy difference, the fragmentation energies and the electron amnities show that Fe（MgO）4 and Fe（MgO）6 possess relatively higher stabilities. The HOMO-LUMO gaps of Fe（MgO）n decrease obviously as compared with （MgO）n. Almost equal unpaired electrons of the 3d state of the Fe atom in Fe（MgO）n result in a nearly equal magnetic moment of Fe（MgO）n.     

Tm Mössbauer effect and magnetic study of Tm6Mn23 and its ternary hydride

The magnetic properties and the lattice constants of Tm₆Mn₂₃ were determined before and after hydrogen absorption. The compound Tm₆Mn₂₃ is ferrimagnetic with an ordering temperature T_c = 404 K. After hydrogen absorption the magnetization is strongly reduced and does not point to the occurrence of magnetic ordering. The strongly increasing hyperfine splitting observed by means of ¹⁶⁹Tm Mössbauer spectroscopy in the hydride for temperature below 60 K, however, shows that the Tm sublattice becomes magnetically ordered after H₂ absorption as well. In uncharged and charged Tm₆Mn₂₃ the values of the Tm moments are close to the free ion values.     

Magnetic and electronic structure calculations of antiferromagnetic Mn2As

Magnetic and electronic structure calculations are performed for Mn₂As with antiferromagnetic (AFM), ferromagnetic (FM), and ferrimagnetic (FIM) spin ordering, using the full-potential linearized augmented plane-wave (FLAPW) method based on the generalized gradient approximation (GGA). It is shown that AFM is the magnetic ground state of Mn₂As, which is in agreement with the experimental observations. At a low temperature (0 K), AFM-FIM transition is also predicted which is consistent with the previous predictions. The ground state stability of the magnetic structure of Mn₂As is attributed to the nearest Mn (I) and Mn (II) antiferromagnetic interaction. The calculated magnetic moment of Mn (II) is found to be in good agreement with the neutron diffraction experiment while there is a disagreement for the magnetic moment of Mn (I). The different magnetic moments are reflected in the electronic structures of Mn₂As and the exchange splitting between Mn atoms is shown to be an intra-atomic effect.     

169Tm Mössbauer effect and magnetic study of Tm6Mn23 and its ternary hydride

The magnetic properties and the lattice constants of Tm₆Mn₂₃ were determined before and after hydrogen absorption. The compound Tm₆Mn₂₃ is ferrimagnetic with an ordering temperature T_c = 404 K. After hydrogen absorption the magnetization is strongly reduced and does not point to the occurrence of magnetic ordering. The strongly increasing hyperfine splitting observed by means of ¹⁶⁹Tm Mössbauer spectroscopy in the hydride for temperature below 60 K, however, shows that the Tm sublattice becomes magnetically ordered after H₂ absorption as well. In uncharged and charged Tm₆Mn₂₃ the values of the Tm moments are close to the free ion values.     

Stability of ferrimagnetic multilayers

We study the field induced instability of the ground state of ferrimagnetic multilayers consisting of a stacking alternating two different uniaxial ferromagnetic layers. For multilayers with even number of layers N, we obtain analytical expressions for the critical fields in terms of the magnetic parameters (anisotropies, and interlayer exchange coupling), for any value of N. The critical fields are calculated from the energy fluctuations for small variations in the equilibrium magnetic profile. The form of the hysteresis curves is discussed, using the expressions of the critical fields.     

Room-Temperature Ferromagnetic ZnMnO Thin Films Synthesized by Plasma Enhanced Chemical Vapour Deposition Method

Room-temperature ferromagnetic Mn-doped ZnO films are grown on Si （001） substrates by plasma enhanced chemical vapour deposition （PECVD）. X-ray diffraction measurements reveal that the Znl-xMn.O films have the single-phase wurtzite structure. X-ray photoelectron spectroscopy indicates the existence of Mn^2＋ ions in Mndoped ZnO films. Furthermore, the decreasing additional Raman peak with increasing Mn-doping is considered to relate to the substitution of Mn ions for the Zn ions in ZnO lattice. Superconducting quantum interference device （SQUID） measurements demonstrate that Mn-doped ZnO films have ferromagnetic behaviour at room temperature.     

(OsnN)0,±(n=1-6)团簇电子结构与光谱性质的理论研究

采用密度泛函理论中的杂化密度泛函B3LYP方法在赝势基组LANL2DZ水平上对Os_nN^0,±(n=1-6)团簇的各种可能构型进行了几何结构优化,得出了它们的基态构型,并对基态结构的磁学性质、自然键轨道(NBO)、光谱和芳香性进行了理论研究. 研究结果表明:OsN^-和Os₅N^-团簇发生了"磁矩猝灭"的现象,在Os₂N和Os₄N< 关键词： nN^0,±(n=1-6)团簇')" href="#">Os_nN^0,±(n=1-6)团簇 电子结构 光谱性质 密度泛函理论     

Magnetism of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> manganite in structurally ordered and disordered states

The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn₂]O₄ and disordered Li_{1 − δ}Mn_δ[Mn_{2 − δ}Li_δ]O₄ (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E _eff ≥ 1 MeV) with a fluence of 2 × 10²⁰ cm⁻² at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn₂O₄ manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.