新型（Pb,Cd）—1222相化合物的制备,结构和电学性质

本成功地合成了一系列新型Ｐｂ－１２２２相层状铜氧化物（Ｐｂ０．５Ｃｄ０．５）（Ｓｒ０．９Ｒ０．１）２（Ｒ‘０．７Ｃｅ０．３）２Ｃｕ２Ｏｚ，Ｒ＝Ｒ’＝Ｙ，Ｐｒ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｈｏ以有（Ｒ，Ｒ‘）＝（Ｌａ，Ｅｕ），Ｓｍ，Ｇｄ），（Ｓｍ，Ｅｕ），（Ｌａ，Ｇｄ），（Ｅｕ，Ｇｄ），（Ｎｄ，Ｄｙ），（Ｎｄ，Ｙ），（Ｎｄ，Ｅｒ）。     

新型（Pb，Cd）－1222相化合物的制备、结构和电学性质

本文成功地合成了一系列新型Ｐｂ－１２２２相层状铜氧化物（Ｐｂ０．５Ｃｄ０．５）（Ｓｒ０．９Ｒ０．１）２（Ｒ＇０．７Ｃｅ０．３）２。Ｃｕ２Ｏｘ，Ｒ＝Ｒ＇＝Ｙ，Ｐｒ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｈｏ以及（Ｒ，Ｒ’）＝（Ｌａ，Ｅｕ），（Ｓｍ，Ｇｄ），（Ｓｍ，Ｅｕ），（Ｌａ，Ｇｄ），（Ｅｕ，Ｇｄ），（Ｎｄ，Ｅｕ），（Ｎｄ，Ｄｙ），（Ｎｄ，Ｙ），（Ｎｄ，Ｅｒ）．Ｘ－射线衍射和电子衍射表明它们属于四方晶系，其结构与（Ｐｂ，ＣＵ）－１２２２相结构相似．其中（Ｒ＇，Ｒ＇）＝（Ｅｕ，Ｇｄ）的样品在氧气中成相得到２３Ｋ的超导转变临界温度．     

SCF—Xα—SW程序和LMTO程序的改进及其在固体体系中的应用

在ＹＨ－１／ＹＨ－２计算机上将多重散射Ｘα自洽场方法（ＳＣＦ－Ｘα－ＳＷ）程序和线性Ｍｕｆｆｉｎ－ｔｉｎ轨道方法（ＬＭＴＯ）程序做了改进，实现了向量化和并行化。研究了Ｃ６０的能级；计算了苯分子从１ｅ１ｇ，２ｅ２ｇ和１ａ２ｕ开始激发的１０８个Ｒｙｄｂｅｒｇ态单电子轨道激发能，即１ｅ１ｇ，２ｅ２ｇ，１ａ２ｕ→ｋａ１ｇ（ｋ＝３－１１），ｋｅ２ｇ（ｋ＝２－７），ｋｅ１ｕ（ｋ＝３－８），ｋｅ１ｇ（ｋ＝３－５     

硝酸稀土-邻菲罗啉-甘氨酸三元配合物的合成及其表征

合成了ＲＥ（Ｐｈｅｎ）２（Ｇｌｙ）（ＮＯ３）３．３Ｈ２Ｏ（其中ＲＥ＝Ｌａ,Ｃｅ,Ｐｒ,Ｎｄ,Ｇｄ,Ｓｍ,Ｅｒ,Ｙ;Ｐｈｅｎ＝邻菲罗啉;Ｇｌｙ＝甘氨酸）固体配合物,对所合成的配合物进行元素分析、摩尔电导、ＩＲ、ＵＶ、ＴＧ－ＤＴＡ等的分析测试,初步研究了配合物的组成,结构及性质。     

在小硅化物SiX^m（X=Be,B,C,N,O,F,Ne,m=～4—＋2）中分子成…

此文用从头计算法，在ＨＦ，ＭＰ２，ＭＰ３水平下，使用基组６－３１Ｇ，６－３１＋Ｇ对ＳｉＯ的等电子分析ＳｉＸ＾ｍ（Ｘ＝Ｂｅ，Ｂ，Ｃ，Ｎ，Ｆ，Ｎｅ，ｍ＝－４～＋２）进行了几何优化，并计算了相应的平衡几何构型下的振动频率，对ＳｉＯ分子，使用ＱＣＩＳＤ（Ｔ）方法考虑了不同水平下的电相关效应，并考虑了不同其函数６－３１＋Ｇ和６－３１１＋Ｇ的影响。计算结果表明，所有分子的势能曲线都有稳定的极小值，并且键长与频     

在SrTiO3、LaAlO3和Y-ZrO2衬底上外延生长La1.85Sr0.15CuO4、La2CuO4和Nd1.85Ce0.15CuO4、Pr2CuO4薄膜

利用脉冲激光法研究了在（１００）ＳｒＴｉＯ３（ＳＴＯ）、（１００）ＬａＡｌＯ３（ＬＡＯ）和（１００）Ｙ－ＺｒＯ２（ＹＳＺ）衬底上外延生长ＬａＣｕＯ４（ＬＣＯ）,Ｌａ１．８５Ｓｒ０．１５ＣｕＯ４（ＬＳＣＯ）,Ｎｄ１．８５Ｃｅ０．１５ＣｕＯ４（ＮＣＣＯ）和Ｐｒ２ＣｕＯ４（ＰＣＯ）薄膜的工艺技术。利用Ｘ光衍射仪检测了不同条件下制备的薄膜样品结构和取向。Ｘ射线衍结果表明,在事适的制膜条件下可以在这三种衬底     

DCP－直读光谱法测高纯氧化镧中的Ce、Pr、Nd和Sm

本文提出用ＤＣＰ—ＡＥＳ方法直接测定高纯Ｌａ２Ｏ３中的Ｃｅ，Ｐｒ，Ｎｄ和Ｓｍ。方法简便、快速。检出限分别为Ｃｅ，０．０１２μｇ／ｍｌ；Ｐｒ，０．０２１μｇ／ｍｌ；Ｎｄ，０．０２１μｇ／ｍｌ以及Ｓｍ，０．００９μｇ／ｍｌ。     

在Ar和Xe低温基体中Fe（CO）3与CO扩散控制反应研究

本文用２８０ｎｍ脉冲激光光解被Ａｒ和Ｘｅ基体隔离的Ｆｅ（ＣＯ）５以产生配位不饱和的Ｆｅ（ＣＯ）３。用傅里衰变换红外光谱仪实时监察光解停止后Ｆｅ（ＣＯ）３和ＣＤ的复合，并以Ｓｍｏｌｕｃｈｏｗｓｋｉ扩散控制反应动力学理论模型求得Ｆｅ（ＣＯ）３与ＣＯ的反应半径为４．０×１０＾－１０ｍ，ＣＯ在１０Ｋ的Ａｒ和Ｘｅ基体中的扩散系数分别为２．２×１０＾－２３ｍ＾２／ｓ和４．５×±∩＾－２３ｍ＾２／ｓ。     

DCP—直读光谱法测高纯氧化镧中的Ce,Pr,Nd和Sm

本文提出用ＤＣＰ－ＡＥＳ方法直接测定高纯Ｌａ２Ｏ３中的Ｃｅ，Ｐｒ，Ｎｄ和Ｓｍ。方法简单、快速。检出限分别为Ｃｅ，０．０１２μｇ／ｍｌ；Ｐｒ，０．０２１μｇ／ｍｌ；Ｎｄ，０．０２１μｇ／ｍｌ以及Ｓｍ，０．００９μｇ／ｍｌ。     

分子束外延Zn_（1－x）Cd_xSe／ZnSe超晶格的拉曼光谱

运用分子束外延（ＭＢＥ）技术成功地生长出Ｚｎ１－ｘＣｄｘＳｅ／ＺｎＳｅ超晶格，并对不同的样品进行了拉曼散射光谱的测试。获得了多达５级的ＺｎＳｅ的ＬＯ声子峰和ＺｎＳｅ的ＴＯ声子峰；同时还在频移为１４４ｃｍ－１、３７０ｃｍ－１处观测到了两个新声子峰，估计是来自于ＺｎＣｄＳｅ的声学模和光学模。     

稀土硅钨杂多配合物与半菁复合材料的合成及光学性质

通过Keggin结构稀土硅钨杂多配合物K₁₃[Ln(SiW₁₁O₃₉)₂] (其中Ln=La,Ce,Pr,Nd,Sm,简写为Ln(SiW₁₁)₂)与碘化(E)-N-甲基-4-(2-(4-二甲氨基苯基)乙烯基)吡啶(C₁₆H₁₉N₂I,AI)反应,制备了一系列含轻稀土元素的硅钨杂多配合物与半菁衍生物的复合材料。应用元素分析和TG-DTA确定配合物的组成为(C₁₆H₁₉N₂)₁₀K₃[Ln(SiW₁₁O₃₉)₂]。利用红外光谱、紫外-可见光谱和荧光光谱研究了上述复合材料的光学性质及复合材料中无机组分与有机组分间的相互作用。     

Structural Study of Lanthanide Complexes Formed with o-Vanillin Salicyloylhydrazone and o-Vanillin Paraanisidine

Abstract

Ten lanthanide complexes (Ln=La, Ce, Pr, Nd, Sm, Gd, Eu and Dy) with the title ligands have been synthesised and characterised. The structure of these complexes are assigned on the basis of IR spectra, magnetic and thermal analysis data. The IR spectra indicate that o-vanillin paraanisidine (oVPA) is a bidentate ligand coordinating through azomethine N and phenolic O whereas o-vanillin salicyloylhydrazone (oVSH) is tridentate possessing ketonic O as an additional donor site. Involvement of anions (Cl^?, Ac^?) in coordination is explored. Electronic spectra indicate weak covalent nature of metal ligand bond and various parameters β, b½, η and δ have been evaluated.     

钙钛矿型稀土镓酸盐的光谱性质

本文得到LaGaO3晶体室温下的激发光谱和荧光光谱,发现LaGaO3晶体能够产生可见荧光,并且荧光谱线比粉末状LaGaO3变窄.测定了室温下LnGaO3(Ln=La,Pr,Na)晶体的吸收光谱,对红外吸收光谱给出了理论点阵振动数目和对称类型,研究了晶体经退火处理对吸收光谱的影响.对粉末状 LaGaO3:Ln(Ln=Ce,Sm,Tb)研究了合成温度及掺杂稀土离子浓度对光谱结构的影响.     

香兰素对甲苯胺希夫碱稀土配合物的红外光声光谱

研究了香兰素对甲苯胺希夫碱及其金属配合物在３８００－２００ ｃｍ＾－１范围的傅里叶变换红外光谱光谱，对主要谱带进行了经验归属。     

Synthesis and Spectral Characterization of Methyl‐2‐pyridyl Ketone Benzoyl Hydrazone and Its Complexes with Rare Earth Nitrates

Abstract

The hydrazone ligand, methyl‐2‐pyridyl ketone benzoyl hydrazone (L), and its complexes with rare earth nitrates have been synthesized. These new complexes with the general formula of Ln(L)₂(NO₃)₃ · nH₂O (where Ln=La, n=5.5; Ce, Pr, n=5; Nd, Eu, n=4) were characterized by mass spectra, elemental analysis, IR spectra, thermal analysis, UV spectra, molar conductivity, and luminescent spectra. All the complexes are stable in air. The results show that the lanthanide ions in each complex are coordinated through oxygen and nitrogen atoms of the ligand, the oxygen atoms of the nitrate, and coordinated water molecules. The amide‐oxygen atoms of L coordinate to the Ln ions in its keto‐form. Tentative structures for the complexes have been proposed.     

Phase transitions of lanthanide monophosphides with NaCl-type structure at high pressures

Lanthanide monophosphides LnP (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Tm and Yb) with a NaCl-type structure have systematically been prepared at high temperatures. Using synchrotron radiation, X-ray diffractions of LnP have been studied up to 61 GPa at room temperature. The NaCl---CsCl transition for CeP is found at around 25 GPa. First-order phase transitions of LnP (Ln = La, Pr and Nd) with the crystallographic change occur at around 24, 26 and 30 GPa, respectively. The structure of the high pressure phases of these phosphides is a body center tetragonal structure (Ln: 0, 0, 0; P: 1/2, 1/2, 1/2; space group P4/mmm), which can be seen as the distorted CsCl-type structure. The Pr---P distance in the high pressure form of PrP is 2.789 Å. This almost agrees with the sum of covalent radii of Pr and P. The Pr---P bond has the covalent character at very high pressures. Similar results are also obtained for LaP and NdP. The pressure-induced phase transitions of SmP, GdP, TbP, TmP and YbP occur at around 35, 40, 38, 53 and 51 GPa, respectively. The structure of the high pressure phase is unknown. The phase transitions of LnP with many f-electrons are not due to the mechanism of the ordinary NaCl---CsCl transition. The transition pressures of LnP increase with decreasing the lattice constants in the NaCl-type structure, which decrease with increasing atomic number of the lanthanide atoms.     

稀土离子掺杂纳米TiO_2的太赫兹光谱研究

对sol-gel法制备的不同稀土元素(Ce,Nd,Sm)掺杂的纳米TiO2粒子进行研究。X射线衍射(XRD)和X射线光电子能谱(XPS)分析结果表明,稀土离子均以间隙的形式均匀分布在纳米TiO2晶格内。傅里叶变换红外光谱(FTIR)和太赫兹时域光谱(THz-TDS)显示,掺杂TiO2较纯TiO2具有更强的红外活性;在0.2~1.70 THz波段,TiO2的折射率随着频率的增加而减小,并呈现反常色散现象;Ce掺杂引起新的特征吸收,分别为1.35和1.58 THz,且造成太赫兹吸收谱的吸收边发生红移,Nd和Sm掺杂则造成吸收边蓝移。在0.2~1.7 THz范围内,Sm掺杂引起的介电损耗角正切值(taneδ)最小,其平均值为0.05。     

Combined Study of Structural,Magnetic and Transport Properties of Eu_(0.5)Ln_(0.5)BiS_2F Superconductor

Superconductivity below 0.3 K and a charge-density-wave-like(CDW-like) anomaly at 280 K were observed in EuBiS_2F recently.Here we report a systematic study of structural and transport properties in Eu_(0.5)Ln_(0.5)BiS_2F(Ln=La,Ce,Pr,Nd,Sm) by electrical resistivity,magnetization,and specific heat measurements.The lattice constants have a significant change upon rare earth substitution for Eu,suggesting an effective doping.As Ln is changed from Sm to La,the superconducting transition temperature T_c increases from 1.55 K to 2.8 K.In contrast to the metallic parent compound,the temperature dependence of electrical resistivity displays semiconductinglike behavior for all the Eu_(0.5)Ln_(0.5)BiS_2F samples.Meanwhile,the CDW-like anomaly observed in EuBiS2F is completely suppressed.Unlike the mixed valence state in the undoped compound,Eu ions in these rareearth-doped samples are mainly divalent.A specific anomaly at 1.3 K resembling that in EuBiS2F suggests the coexistence of superconductivity and spin glass state for Eu_(0.5)La_(0.5)BiS_2F.Coexistence of ferromagnetic order and superconductivity is found below 2.2 K in Eu_(0.5)Ce_(0.5)BiS_2F samples.Our results supplies a rich diagram showing that many interesting properties can be induced in BiS_2-based compounds.     

Synthesis,characterization, luminescence properties and antioxidant activity of Ln(III) complexes with a new aryl amide bridging ligand

A novel Aryl amide ligand H₂L and its eight complexes, [LnH₂L(NO₃)₂·H₂O]NO₃ [Ln=Sm(III), Er(III), Tb(III), Dy(III), La(III), Gd(III), Nd(III), and Pr(III)], are presented. The ligand and complexes were synthesized and characterized based on elemental analyses, molar conductance, IR, ¹H and ¹³C-NMR, UV–VIS., and TGA studies. The conductivity data show a 1:1 electrolytic nature with a general formula [LnH₂L(NO₃)₂·2H₂O]NO₃ The IR spectra reveal coordination of the ligand through the azomethine nitrogen and the phenolic hydroxyl of the ligand to the lanthanide ion. The coordinated nitrate ions behave in a bidentate fashion. The thermal decomposition studies indicate the presence of two water molecules in the inner coordination sphere. Under the excitation at 319 nm, the luminescence emission properties for Sm, Tb, and Dy complexes are observed. These observations show that the ligand favors energy transfers to the emitting energy level of these lanthanide ions. Furthermore, the antioxidant activity of the ligand and its Ln(III) complexes was determined by DPPH radical scavenging method, which indicates that the Ln(III) complexes exhibit more effective antioxidant activity than the ligand alone.     

Magnetic susceptibility and electrical resistivity of some Th2Zn17-type rare-earth zinc phases

We report measurements of the magnetic susceptibility and electrical resistivity of the iostructural compounds RE₂Zn₁₇ (RE=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The composition dependence of the lattice parameter and effective moment indicate that all the RE ions are trivalent except Yb which is divalent. Magnetic order is observed in compounds where RE=Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er. A second transition is seen for RE=Pr, Ho, Sm and Tb. Superzone boundary effects are observed in the electrical resistivity of these four alloys as well as in Er₂Zn₁₇. Resistivity measurements reveal concentrated Kondo behavior (or 4f instability) of Ce in Ce₂Zn₁₇.