V12M团簇的电子结构和磁性的第一性原理研究

采用密度泛函理论框架下的广义梯度近似（DFT／GGA），对V13团簇及V12M掺杂团簇（M=Sc，Ti，Cr，Mn，Fe，Co，Ni，Y，Zr，Nb，Mo，Tc，Ru）的电子结构和磁性进行研究．通过对团簇的基态几何构型优化计算得到了团簇束缚能、电子结构以及磁矩的大小，系统地分析了V13和V12M团簇磁矩的形成机理以及电子结构与磁性的变化关系．发现掺杂团簇V12Fe和V12Ru为具有大束缚能和大能隙间隔的闭壳电子结构，V12Y团簇具有11μB的大磁矩，而其它掺杂团簇则表现为弱磁性．     

Ni50Mn37In13磁驱动形状记忆合金薄膜中的交换偏置

研究了磁场冷却前后Ni50Mn37In13磁驱动形状记忆合金薄膜在低温下的磁学行为。结果表明:磁场冷却后的Ni50Mn37In13薄膜在10 K温度下表现出一定的交换偏置效应。在特征温度Tf以下,零场冷却状态下的Ni50Mn37In13合金处于超自旋玻璃态,而经磁场冷却后发生了从自旋玻璃态向磁有序的超铁磁结构的变化。超铁磁结构中的超铁磁团簇与反铁磁基体构成了铁磁/反铁磁耦合,从而导致了交换偏置的产生。     

铁原子簇的交换劈裂和磁性研究

用ＭＳ－Ｘα方法研究了Ｆｅ８原子簇和Ｆｅ１５原子簇的电子结构。结果表明：１两种原子簇中的Ｆｅ原子磁矩及其ｄ能带中的交换劈裂性质互不相同；２．两类原子 的电分布不是均匀的，电荷倾向于从外围原子向内部原子上转移，并且被转移电子的自旋方向与原子簇的对称性质密切在。     

单分散Ni球制备及Ni／NiO的磁性研究

使用微波辅助Poly方法制备了直径范围在100nm～180nm单分散的Ni球，用磁力显微镜（MFM）测其磁结构。进一步对Ni球表面氧化获得了高度球化的NicoreNiOshell结构，采用XRD，TEM，XPS和EDAX对其进行了测量分析，并用VSM和SQUID进一步讨论了铁磁／反铁磁的界面耦合效应。同时，估算了磁性交换偏置耦合场与颗粒尺寸的关系。     

合金相团簇规律及其在Zr-Al-Ni非晶体系中的应用

研究多个典型非晶形成体系合金相结构中的团簇规律,指出在合金相结构中团簇之间以不同方式共享原子的事实。共享后的有效团簇到合金相的连接方式有两种,一种是共享后的团簇成分就是相成分,无须连接原子,另一种是共享后的团簇加上连接原子才能构成空间相结构(这类相称之为团簇相)。这种方法使得对合金相的结构有了一个全新的理解。在典型的非晶形成体系Zr-Al-Ni中,团簇相有3个:AlNiZr-Fe2P结构,Al2NiZr6-InMg2结构和Al5Ni3Zr2-Mn23Th6结构。通过此项工作还提出了基于合金相结构来确定与非晶形成相关的团簇的方法,即与非晶相关的团簇一般为团簇相里出来的孤立团簇,这一结论在Zr-Al-Ni体系中得到了很好的验证。     

Mg和Cu在Al-Zn-Mg合金时效初期的Monte Carlo模拟

采用Monte Carlo方法模拟研究Al-6Zn-(2Mg)和Al-10Zn-1.9Mg-(1.7Cu)合金时效初期微观结构的演变过程,并分析Mg和Cu的基本作用。结果表明:时效初期,Al-6Zn合金中的Zn原子有较强的团聚倾向,形成了明显的Zn原子簇;而在Al-6Zn-2Mg合金中出现明显的Zn原子簇、Zn-Mg原子簇及少量的Mg原子簇。Mg的作用是通过Mg和Zn原子间强烈的相互作用形成Zn、Mg原子交替排布的短程有序结构。含铜的Al-10Zn-1.9Mg-1.7Cu合金中,不仅形成了Zn原子簇、Mg原子簇和Zn-Mg原子簇,还形成了少量Zn-Cu原子簇、Mg-Cu原子簇和Zn-Mg-Cu原子簇。Cu的存在促进Zn原子和Zn-Mg原子团簇化,但对Mg原子的团簇化影响不大。     

半导体ZnS:Co的电子结构与磁性研究

采用基于密度泛函理论的第一性原理方法,研究了闪锌矿结构Co掺杂ZnS体系的电子结构和磁性。通过计算掺杂后组态的几何参数、形成能、磁矩、电子态密度以及电荷密度,发现单个Co原子掺杂,替换超晶胞(2×2×2)中心的Zn原子后体系形成能小于0,可以实现掺杂,且在费米能级处出现自旋极化现象,体系具有半金属特性。通过对2个Co原子的掺杂情况的计算,发现Co-S-Co反铁磁耦合、Co-S-Zn-S-Co铁磁耦合时体系最稳定,同时解释了Co掺杂ZnS体系的铁磁性产生机理。     

近共晶成分Ni-P非晶合金微结构特征的原子模拟分析

采用分子动力学方法模拟了Ni_(100-x)P_x(x=19.0、19.4、19.6、19.8、20.0、21.0)合金在冷速为5×10~(12)K/s下的快速凝固过程,并采用Voronoi多面体指数n_3,n_4,n_5,n_6和团簇类型指数(Zn_i/(ijkl)_i…)对其局域原子结构进行了表征。结果发现,Ni原子的团簇属性主要是高配位(Z≥12)的Frank-Kasper团簇及其变形结构,典型的化学短程序为NiZ-2P3,基本团簇间可通过交叉共享(IS)联结形成中程序结构;而P原子的局域结构除了Z=10的BSAP多面体外,还存在大量高配位(特别是Z=12)的Frank-Kasper结构形态,典型的化学短程序为Ni_(12)P;并且,P芯基本团簇的壳层原子全部为Ni,其间只能通过顶点共享(VS)、边共享(ES)和面共享(FS)联结形成扩展团簇。BSAP多面体及其相关结构被证实对Ni_(100-x)P_x非晶合金的形成具有重要影响,其数量在共晶点x=19.6时最多,偏离共晶点越远,所占比例越小,其结果与不同浓度下Ni_(100-x)P_x合金非晶形成能力的变化趋势一致。这可能就是Ni-P合金在共晶点具有最强非晶形成能力的原因。     

Heusler合金Ni2MnGa磁性微观机理的第一性原理

采用量子力学计算软件包研究了单晶Heusler合金Ni2MnGa的结构参数、磁矩、四方变形以及磁性微观机理,并将计算结果与实验值和其它理论计算值进行了比较.计算所得的结构参数和磁矩相对于局域自旋密度近似值而言,与实验值符合得更好.四方变形中,发现磁矩在c/a=1附近有一个尖锐的最小值,在c/a≈0.94处有一个局域最大值,此磁矩的局域最大值对应着一个稳定的马氏体.总磁矩随c/a的变化主要来自Ni原子:由于一个原胞中有两个Ni原子对其总磁矩作了贡献,因而屏蔽了Mn原子的贡献所致.对总态密度的分析表明,自旋向上的态密度位于费米面以下,而自旋向下的态密度有两个主峰,分别位于费米面两侧,这是磁有序合金的一个典型特性.且合金磁性主要源于Mn原子的d-eg和d-t2g亚带,这与实验结果一致.     

Ni掺杂CoFe_2O_4晶体电磁性质的第一性原理研究

尖晶石型钴铁氧体因具有良好的电磁性质,广泛应用于电子装备、微波装备及高密度磁存储等领域。采用基于密度泛函理论(DFT)的第一性原理平面波赝势法,结合广义梯度近似(GGA+U),系统研究不同Ni掺杂量对CoFe_2O_4晶体结构、电子结构和磁性能的影响。结果表明:Ni离子倾向于占据八面体位置且随着Ni掺杂量的增加,晶格常数呈递减趋势。通过电子结构分析表明,带隙随着Ni掺杂量的变化而变化,大部分都呈绝缘体,且存在强烈的3d-2p轨道杂化。磁性能依赖于Ni掺杂量,随着Ni掺杂量的增加,晶格中的原子磁矩变化不明显,但总磁矩呈线性递减趋势,这主要是因为Ni离子最外层的3d未配对电子数与Co离子最外层3d未配对电子数不同,因而对磁性能的影响较大。     

Magnetism and work function of Ni-Cu alloys as metal gates

The magnetism and work function of pure Ni(001) and Ni-Cu slab alloys were investigated using first-principles methods based on density functional theory. The calculated results reveal that both magnetic moments and work functions of the alloys depend strongly on the surface orientation, but hardly on the distribution of doped Cu atoms for a given surface orientation. It is found that the doped Cu atoms have evident influence on the magnetic moment of Ni-Cu slabs, and the average magnetic moment of Ni atoms for Ni-Cu alloys decreases with increasing concentration of Cu atoms. Moreover, it is observed that the work function of Ni(001) is insensitive to the supercell thickness and the inner concentration of Cu atoms. In the meantime, the spin polarization is found to have an obvious role on the work function of the Ni-Cu alloys, which may give a new way to modulate the work function of the metal gate.     

Magnetic behaviour of exposed and embedded nanoclusters

Cluster-assembled films made by depositing nanoscale Fe clusters from a UHV-compatible gas aggregation source have been studied in situ using STM, X-ray dichroism and magnetometry. We follow the evolution of the properties of the films supported on substrates and exposed in UHV, as a function of cluster size and coverage. The STM images show that there is no significant diffusion of the Fe clusters deposited onto Si(111) surfaces at room temperature and that dense films of clusters do not coalesce but maintain their granular nature, X-ray magnetic circular dichroism measurments show that isolated 300-atom clusters adsorbed on graphite have an orbital moment per atom that is double the bulk value and a spin moment enhanced by 4% giving a total moment 10% greater than the bulk. Both moments tend towards the bulk value as either the cluster size or the density of clusters on the surface increases. The isolated clusters are superparamagnetic above 10K but the films have an increasing magnetic remanence at higher temperatures as the cluster density is increased. Thick cluster films have a strong in-plane anisotropy. Films of Fe clusters embedded in Cu and Ag show a giant magneto-resistance that peaks sharply with volume fraction.     

Long-range magnetic order displayed by a bimetallic pentanuclear cluster complex [(Ni(2,2′-bipy)2)3(Fe(CN)6)2]·13H2O and by a Cu(II) analog

A bimetallic pentanuclear cluster complex contains three bis(2,2′-bipyridine)nickel(II) moieties bridged, through two vacant cis-positions around each nickel, to two separate hexacyanoferrate(III) groups via NiNCFe linkages. Freshly prepared crystals of this compound contain 17 water and two dimethylformamide molecules of solvation per cluster. Loss of some solvent molecules is rapid in air, the resulting ‘partly desolvated’ material showing intracluster ferromagnetic coupling and a S=4 ground state, but without long-range magnetic order. In contrast, a rapidly precipitated powder sample, containing 13 waters of hydration [(Ni(2,2′-bipy)₂)₃(Fe(CN)₆)₂]·13H₂O, displays long-range order at a T_C of 11 K. Inter-cluster interactions occur via the H-bonded water pathways which join neighbouring Fe(CN)₆³⁻ groups in separate clusters. Thus, a new example of inter-cluster magnetic ordering has been achieved. A copper(II)-bipy analog also shows long-range order, with T_C of 13 K. In the absence of a crystal structure, the magnetic and spectral properties of this Cu derivative point to a different structural topology being present.     

Mg_3N_2团簇吸附H的密度泛函理论研究

运用密度泛函理论(DFT)中的杂化密度泛函B3LYP方法在6-311G*基组水平上对Mg_3N_2H_m(m=1~4)和(Mg_3N_2)_nH_m(n=2~4,m=1~2)团簇的可能几何结构进行优化,预测了其最稳定结构,并对最稳定结构的电子结构,成键特性,电荷分布,振动特性及稳定性等进行分析。结果表明:当团簇吸附H原子少于N原子数目时,一般形成-NH基;随着团簇吸附H原子数目的增加,当所有N原子吸H形成-NH基后,才有-NH基吸附H原子形成-NH_2基;但并不是所有-NH基全部形成-NH_2基的饱和结构,此时部分H原子会吸附于Mg原子上形成MgH结构。H原子易吸附于凸出的、包含孤对电子的N原子上;由于孤对电子间的排斥作用,H原子的吸附位置呈相互远离趋势。团簇中N-H之间是共价键作用,而Mg-H间是离子键作用,-NH和-NH_2基在团簇中保持完整性,团簇可以很好地描述晶体的储氢行为。     

强磁场下Al-Ni合金凝固初生相Al3Ni的取向行为

进行了10T强磁场下Al-(8%~12%)Ni(质量分数)合金凝固实验,考察了初生相Al3Ni的取向行为。结果表明,加磁场后纤维状初生相Al3Ni在垂直于磁场方向的平面上定向排列聚集,形成层间距基本相同的分层组织。X射线衍射结果表明,施加磁场后,Al3Ni晶体发生了取向,其〈00l〉晶向转向磁场方向。在合金两相区中,当磁感应强度和温度提高到一定值时,初生相的取向程度显著增加,其定向排列因子Г也随之增加。此外,还对晶体在磁场中的取向行为进行了热力学分析。     

Electronic structure and magnetism of PrNixPt1−x compounds

We have studied influence of the Pt–Ni substitution on the crystal structure and magnetic behavior of the PrNi_xPt_1−x compounds. Polycrystalline samples with x = 1, 0.9, 0.75, 0 were prepared and characterized by X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM). The analysis of XRPD data confirmed that the orthorhombic CrB-type structure owned by the parent binary compounds remains conserved through the entire series. The samples were subsequently investigated by specific heat (C_p), magnetization (M) and ac susceptibility measurements in the temperature range 2–350 K and in magnetic fields up to 9 T. All compounds were found to order ferromagnetically. The T_C values monotonously increase with increasing Ni content. To inspect the crystal-field (CEF) effects and magnetocaloric properties specific-heat data were analyzed in detail and the magnetic contribution to the specific heat together with the magnetic entropy have been determined. The results of first principles electronic structure calculations of the PrNi and PrPt confirmed that besides the stable Pr magnetic moments due to localized 4f-electrons only a very small magnetic moments of at most 0.2μ_B is induced at the Ni (Pt) site due to the polarized 3d-electron states (5d-electron states) hybridizing with the Pr 5d-electron states, i.e. the Ni (Pt) moment plays only minor role in the total balance of the magnetic moments in these compounds.     

Structural stability of Fe-based topologically close-packed phases

Precipitates of topologically close-packed (TCP) phases play an important role in hardening mechanisms of high-performance steels. We analyze the influence of atomic size, electron count, magnetism and external stress on TCP phase stability in Fe-based binary transition metal alloys. Our density-functional theory calculations of structural stability are complemented by an analysis with an empirical structure map for TCP phases. The structural stability and lattice parameters of the Fe–Nb/Mo/V compounds are in good agreement with experiment. The average magnetic moments follow the Slater-Pauling relation to the average number of valence-electrons and can be rationalized in terms of the electronic density of states. The stabilizing effect of the magnetic energy, estimated by additional non-magnetic calculations, increases as the magnetic moment increases with band filling for the binary systems of Fe and early transition metals. For the case of Fe₂Nb, we demonstrate that the influence of magnetism and external stress is sufficiently large to alter the energetic ordering of the closely competing Laves phases C14, C15 and C36. We find that the A15 phase is not stabilized by atomic-size differences, while the stability of C14 is increasing with increasing difference in atomic size.     

Ductility and magnetism: An ab-initio study of NiAl–Fe and NiAl–Mn alloys

An ab-initio density functional approach is applied to study the magnetism related aspects of ductility for NiAl microalloyed by Fe and Mn. The generalised stacking fault energies of NiAl are calculated for slip interfaces in which some of Ni and Al atoms are replaced by Fe(Mn) atoms. By comparing spin-polarised and nonmagnetic calculation, it is shown that the local magnetic moment of Fe atom impedes a change of the preferred slip system from 〈001〉 to 〈111〉. The opposite effect is found for NiAl–Mn, in which 〈001〉 slip is significantly unfavored. The results are in general in excellent agreement with experimental observations, verifying improved ductility for NiAl–Fe. The differences in slip behavior are correlated with the changes of the local magnetic moments in 〈001〉 and 〈111〉 slipped NiAl.     

Ab initio Studies on Magnetism of 3d Transition Metal Dimers

Ab initio calculations with the self-consistent full-potential linearized augmented-plane-wave method (FLAPW), under generalized gradient approximation, have been carried out to describe the electronic and magnetic properties of 3d transition metal dimers. It predicted the antiferromagneticity of Cr2 and ferromagneticity of other species. The Mn2 dimer was shown to be ferromagnetic coupling with a local magnetic moment of 5μB, retaining the value of its free atom state. The V2 and Ni2 exhibited low spin-polarization with local magnetic moment of only 1μB per atom. On the other hand, Fe2 and Co2 were highly spin-polarized with local magnetic moments of 3 and 2μB.