MAl_(12)(M=Ni、Mn)及其阴离子团簇的几何结构和磁性的计算研究

采用密度泛函理论(density functional theory,DFT)中的广义梯度近似(generalized gradient approximation,GGA)分别对Al_(13)和MAl_(12)(M=Ni、Mn)四种初始结构的中性和一价阴离子团簇进行计算研究.发现中性和阴离子团簇的基态几何结构均保持I_h对称性,并且基态阴离子团簇还具有较高的运动学稳定性.电磁性质计算显示:基态的中性和阴离子NiAl_(12)团簇分别带有2_(μB)、3_(μB)的磁矩,Ni原子的磁性几乎完全淬灭;而MnAl_(12)团簇分别带有7_(μB)、6_(μB)的磁矩,Mn原子的磁矩主要由3d轨道提供.基态团簇的表面原子出现了自旋分裂,与中心原子呈现出铁磁性作用.对垂直电离能和垂直亲和能的分析表明:中心原子被替代之后,团簇的得电子能力和失电子能力都有所降低.     

Half-Heusler合金NiFeSb和NiMnSb的磁性及电子结构的第一性原理研究

用基于密度泛函理论的第一性原理方法,计算了half-Heusler合金NiFeSb和NiMnSb的晶体结构、磁性及电子结构。计算结果表明,磁性原子Fe和Mn在两种合金的总磁矩中贡献最大,在NiFeSb总磁矩中,Ni原子贡献比例接近在NiMnSb中的2倍,而Sb原子的贡献比例是在NiMnSb中的1/5;两种合金的自旋向上能带都具有明显的金属特征,而自旋向下能带有明显的差别;两种合金费米能级以下的总态密度(DOS)主要由Ni-3d 和Fe-3d（Mn-3d）态决定,费米能级以上主要由Fe-3d（Mn-3d）自旋向下部分决定。     

Mn(SiO2)3(M=Fe,Co,Ni;n=1-3)团簇的几何结构、光电性质及磁性

基于密度泛函理论中的广义梯度近似系统研究M_n(SiO₂)₃(M=Fe,Co,Ni;n=1-3)团簇的几何结构、光电性质和磁学性质.结果表明:Fe,Co原子相对于Ni原子更易于在(SiO₂)₃团簇上聚集;通过分析团簇的分裂途径及其产物,发现稳定性较好的氧化硅是一种很好的用于负载过渡金属"岛膜"的载体材料;M_n(SiO₂)₃团簇的能隙恰好位于近红外光谱范围内.通过磁性分析发现,该复合团簇的磁矩主要局域在过渡金属原子周围,而且,Fe₂(SiO₂)₃和Co₃(SiO₂)₃具有相对较大的磁矩,这主要源于过渡金属原子的d轨道间相互耦合.能隙和磁性两方面性质进一步肯定了二氧化硅磁性复合材料在医学界被用作光动力靶向治疗的可观前景.     

Spin–phonon coupling in van der Waals antiferromagnet VOCl

We report magnetization and Raman spectroscopy study on single crystals of VOCl, a van der Waals antiferromagnetic material. Magnetization measurement confirms an antiferromagnetic transition at 79 K and a magnetic easy axis along crystallographic a direction. The temperature-dependent Raman spectrum reveals five peaks at 30 K. Below the Neel temperature TN, the Raman-active modes 247 cm~(-1) and 404 cm~(-1) remarkably deviate from the standard Boltzmann function,which is ascribed to the strong magnetoelastic coupling between spins and phonons. We further observe an anomaly in 383 cm~(-1) mode at around 150 K. This coincides with the broad maximum in VOCl's magnetic susceptibility, suggesting a development of short-ranged magnetic order at this temperature.     

FeMn掺杂AlN薄膜的制备及其特性研究

采用直流磁控共溅射技术, 以Ar与N₂为源气体, 硅片为衬底成功地制备了Fe, Mn掺杂AlN薄膜. 利用X射线衍射和拉曼光谱研究了工作电流、靶基距离等工艺参数的改变对薄膜结构的影响. 利用扫描电子显微镜和能谱分析仪对薄膜的表面形貌和组成成分进行了分析. 利用振动样品磁强计在室温下对Fe, Mn掺杂AlN薄膜进行了磁性表征. Mn掺杂AlN薄膜表现出顺磁性的原因可能是由于Mn掺杂浓度较高, 在沉积过程部分Mn以团簇的形式存在, 反铁磁性的Mn团簇减弱了体系的铁磁交换作用. Fe掺杂AlN薄膜表现出室温铁磁性, 这可能是AlFeN三元化合物作用的结果. 随着Fe 掺杂AlN薄膜中Fe原子浓度从6.81%增加到16.17%, 其饱和磁化强度M_s由0.27 emu·cm^-3逐渐下降到0.20 emu·cm^-3, 而矫顽力H_c则由57 Oe增大到115 Oe (1 Oe=79.5775 A/m), 这一现象与Fe离子间距离的缩短及反铁磁耦合作用增强有关. 关键词： 直流磁控共溅射 氮化铝薄膜 结构 磁性     

Hg2CuTi型Mn2NiGe合金的电子结构、磁性对压力、四方变形的响应

运用基于密度泛函理论的第一性原理方法,研究了Hg2CuTi型 Mn2NiGe合金的电子结构对外加压力的响应以及Mn2NiGe的电子结构、磁性对四方变形的响应．结果表明：i）随着外加压力的增加,因Ni、Mn原子间距的减小而导致杂化程度的增强,使得态密度整体向低能区域移动,同时,态密度幅度整体略有减小;ii）在由奥氏体相到马氏体相的变形中,同样因Ni、Mn原子间距的减小而导致杂化程度的增强,占据态的态密度向低能区域移动,体系的能量降低,同时,成键态向低能方向移动,反键态向高能方向移动,能带变宽,成键作用加强,最终导致在马氏体相中的稳定性增大;iii）在四方变形过程中,Mn2NiGe总磁矩的变化主要由Ni原子磁矩的变化所产生．     

Linear Copper Complex Arrays as Versatile Molecular Strings: Syntheses,Structures, Luminescence,and Magnetism

The defined linear arrangement of metal atoms in discrete coordination complexes or polymers is still one of the most intriguing challenges in synthetic chemistry. These chain arrangements are of fundamental importance, because of their potential applications as molecular wires and single molecule magnets (SMM) in microelectronic devices on a molecular scale. Oligonuclear Group 11 metal complexes with suitable bridging ligands, specifically those that are based on copper as the first choice of a cheap precursor coinage metal, are of particular interest in this regard. This is due to the superior luminescence properties of these linear clusters that often show d¹⁰⋅⋅⋅d¹⁰ interactions in their molecular structures. The combination of Cu^I with heavier coinage metal ions results in tunable emissive arrays that are also stimuli-responsive. Thus, both linear multinuclear Cu^I and linear heteropolymetallic Cu^I/Ag^I as well as Cu^I/Au^I clusters are excellent candidates for applications in molecular/organic light-emitting devices (OLEDs). Alternatively, paramagnetic multinuclear cupric arrays are prominent as potential molecular wires with enhanced magnetic properties through multiple coupled d⁹ centers. This Review covers the whole range of linear multinuclear assemblies of cuprous and cupric ions in complexes and coordination polymers, their syntheses, photophysical behavior, and magnetic properties. Moreover, recent advances in the rapidly progressing field of hetero-Cu^I/Ag^I and Cu^I/Au^I molecular strings are also discussed.     

A New Class of Lanthanide Complexes with Three Ligand Centered Radicals: NMR Evaluation of Ligand Field Energy Splitting and Magnetic Coupling

Combination of three radical anionic Ph-BIAN ligands (Ph-BIAN=bis-(phenylimino)-acenaphthenequinone) with lanthanoid ions leads to a series of homoleptic, six-coordinate complexes of the type Ln(Ph-BIAN)₃. Magnetic coupling data were measured by paramagnetic solution NMR spectroscopy. Combining ¹H NMR with ²H NMR of partially deuterated compounds allowed a detailed study of the magnetic susceptibility anisotropies over a large temperature range. The observed chemical shifts were separated into ligand- and metal-centered contributions by comparison with the Y analogue (diamagnetic at the metal). The metal-centered contributions of the complexes with the paramagnetic ions could then be separated into pseudocontact and Fermi contact shifts. The latter is large within the Ph-BIAN scaffold, which shows that magnetic coupling is significant between the lanthanide ion and the radical ligand. Pseudocontact shifts were further correlated to structural data obtained from X-ray diffraction experiments. Ligand-field parameters were determined by fitting the temperature dependence of the observed magnetic susceptibility anisotropies. The electronic structure determined by this approach shows, that the Er and Tm analogues are candidates for single molecule magnets (SMM). These results demonstrate the possibilities for the application of NMR spectroscopy in investigations of paramagnetic systems in general and single molecule magnets in particular.     

新型二硫纶·菲咯啉-5，6-二酮合铜(Ⅱ)配合物的磁性研究

报道了新合成的二氰基二硫纶·菲咯啉-5，6-二酮合铜(Ⅱ)配合物CuLL′(L=mnt^2-, 1,2-dicyano-1,2-ethylenedithiolate; L′=phen-5，6-dione, 1,10-phenanthroline-5,6-dione)的变温磁化率和电子顺磁共振波谱表征结果. 发现微晶粉体型的标题配合物CuLL′具有一定的顺磁性，形成四配位的近似于方形的结构. 探讨了这种配合物磁学特性与结构的关系.