Mn_(1-x)Zn_xCr_2O_4(0.0≤x≤1.0)晶体结构与磁性研究

通过固相反应法制备了尖晶石氧化物Mn1-xZnxCr2O4(0.0≤x≤1.0)多晶系列样品,并对其晶体结构和磁性进行了系统研究.研究结果表明,系列样品具有立方尖晶石结构,随Zn掺杂浓度x增大,晶格常数单调减小,体系的阻挫因子逐渐增大.低温下MnCr2O4表现为共线亚铁磁和螺旋亚铁磁的共存.当x≤0.4时,随着x增大,4.5T磁场下所测量的磁化强度逐渐减小,矫顽力逐渐增大,表明体系中的螺旋亚铁磁成分逐渐增多.随着x进一步增加,样品x=0.6和0.8表现为自旋玻璃态特征,最终在x=1.0时转变为强阻挫的反铁磁态.     

Ellipsometry study of interband transitions in TlGaS2xSe2(1−x) mixed crystals (0≤x≤1)

In this paper, the spectroscopic ellipsometry measurements on TlGaS_2xSe_2(1?x) mixed crystals (0≤x≤1) were carried out on the layer-plane (001) surfaces with light polarization E⊥c^? in the 1.2–6.2 eV spectral range at room temperature. The real and imaginary parts of the dielectric function, refractive index and extinction coefficient were calculated from ellipsometric data using the ambient-substrate optical model. The critical point energies in the above-band gap energy range have been obtained from the second derivative spectra of the dielectric function. Particularly for TlGaSe₂ crystals, the determined critical point energies were assigned tentatively to interband transitions using the available electronic energy band structure. The effect of the isomorphic anion substitution (sulfur for selenium) on critical point energies in TlGaS_2xSe_2(1?x) mixed crystals was established.     

Ti_(n-m)Zr_mO_(2n)(n=2-7,0≤m≤n)团簇结构和稳定性研究

应用密度泛函理论中的B3LYP方法对Ti_(n-m)Zr_mO_(2n)(n=2-7,0≤m≤n)团簇的基态几何结构、相对稳定性和电子结构进行了理论研究.结果表明,与桥氧链接的Ti原子被Zr原子取代后形成的混合团簇较为稳定;在团簇尺寸一定的条件下(即n相同),随着Zr原子数m的增加,团簇的结合能基本呈线性增大,团簇的稳定性增强;Ti、Zr、O原子之间发生了电荷转移现象,形成了稳定的Ti-O-Zr键.     

Transport properties of the single-crystal La2−xBaxCuO4 (0≤x≤0.11)

We report on the temperature dependence of the in-plane electrical resistivity ρ_ab and the in-plane Hall coefficient R_H in various magnetic fields of the single-crystal La_2−xBa_xCuO₄ with x=0.083 and 0.11. In x=0.11, which is close to x=1/8, where the superconductivity is strongly suppressed, a clear jump in ρ_ab and a drop in R_H have been observed at T_d2∼53 K, where the structural phase transition between the orthorhombic mid-temperature and tetragonal low-temperature phases occurs. Moreover, a sign reversal of R_H has been observed below ∼25 K and the magnitude of the sign reversal increases with increasing magnetic field. In x=0.083, on the other hand, there is neither jump in ρ_ab nor drop in R_H at T_d2, and also no sign reversal in R_H at low temperatures even in magnetic fields up to 9 T. In conclusion, there is no doubt that a static stripe order of holes and spins, observed in La_1.6−xNd_0.4Sr_xCuO₄ with x∼1/8, is formed below T_d2 also in La_2−xBa_xCuO₄ with x∼1/8. The R_H in the stripe-ordered state has a negative value, which is consistent with the recent theory by Prelovšek et al.     

Helimagnetism of CuxZn1−xCr2Se4 (for 0.0 ≤ × ≤ 0.1)

Abstract

The magnetization, the susceptibility and the magnetic anisotropy field of Cu _x Zn_1?xCr₂Se₄ compounds have been studied at low temperatures (down to 2.9 K) in: high magnetic stationary fields (up to 14 T), high pulsed magnetic fields (up to 25 T), medium magnetic stationary fields (up to 0.6 T). The magnetic structure of these spinels was studied by neutron powder diffraction.

The magnetic properties of Cu_xZn_1?xCr₂Se₄ are explained in terms of the molecular field approximation assuming the existence of 90° exchange interactions, ferromagnetic for Cr-Se-Cr between the nearest Cr ions and antiferromagnetic for Cr-Se-Se-Cr between the second-nearest Cr ions. The exchange parameters and integrals for the whole series under consideration are calculated. Taking into account the three magnetic phase transitions observed in these spinels (Juszczyk, Krok, Okońska-Koz?owska, Broda, Warczewski, Byszewski, 1981) and the neutron diffraction studies a modification of the simple spin spiral forced by a strong magnetic field is described.     

Mg_n(2≤n≤15)的几何结构和振动频率及光谱研究

采用基于密度泛函理论的B3LYP方法计算了Mgn(2≤n≤15)团簇的键长、能量、二阶能量差分、配位数、能隙、光谱等性质,找到了Mgn(2≤n≤15)团簇的较稳定结构并确定幻数团簇,然后对这些稳定结构进行光谱分析。采用3-21g和lanl2dz一大一小两种基组分别进行计算,结果表明,两种基组计算结果在基态结构上相差不大,只有二阶能量差分有较小的区别,lanl2dz基组计算的键长偏长;Mg4、Mg10、Mg15为较稳定结构,其中Mg4、Mg10为幻数团簇;除Mg2之外,其他团簇都有红外、拉曼活性;对稳定结构的光谱分析发现,Mg10的红外谱峰最多,Mg15的光谱强度最大。     

Nan(5≤n≤10)小团簇相变

采用紧束缚的分子动力学模型,对Nan(5≤n≤10)小团簇的键长涨落、势能、热容量等熔化性质在50 K～1500 K温区进行了模拟研究,结果表明:它们发生两次相变,一种在230 K～300 K的温度范围内,依次有块体玻璃态转变;一种在550 K～870 K温度段,依次经历了熔化相变.同时也得到随着团簇体系的减小,势能由下向上排列的曲线,即体系的势能由低变高.     

(SiO_2)_n~-(n≤7)团簇的密度泛函研究

采用密度泛函理论中的广义梯度近似对(SiO2)n-(n≤7)负离子团簇的几何构型进行了优化,并对能量和频率进行了计算.通过对计算结果的分析发现,与近邻尺寸的团簇比较,(SiO2)4-团簇最低能量结构更加稳定;(SiO2)n-(n≥4)团簇的最低能量结构是以(SiO2)4-为基础结构,具有一定的生长规律.     

Lithium/vacancy ordering in the monoclinic LixNiO2 (0.50≤x≤0.75) solid solution

Lithium de-intercalation from the nearly stoichiometric LiNiO₂ phase (z=0.02 in Li_1−zNi_1+zO₂) entails a structural transition from the rhombohedral to the monoclinic symmetry. As this macroscopic lattice distortion appears in a wide composition range (0.50<x<0.75, x in `Li_xNiO₂'), a detailed electron diffraction study has been performed on the intermediate Li_0.63Ni_1.02O₂ composition in order to find the driving force of this transition. A superstructure cell, four times bigger than the one deduced from the X-ray Rietveld refinement, has been derived from the electron diffraction data. The existence of such a superstructure is suggestive of a possible ordering of vacancies among the lithium layers. Indeed, the existence of three lithium crystallographic positions in this supercell allows us to understand, on the one hand, why a monoclinic distortion occurs, and, on the other hand, its composition limits (Li_0.50□_0.25□_0.25′NiO₂ and Li_0.50Li_0.25□_0.25′NiO₂). Moreover, the presence of twinned crystals has also been shown in this monoclinic phase and has been related to the structural change which occurs on lithium de-intercalation from the pristine rhombohedral Li_0.98Ni_1.02O₂ phase.     

高离化Kr~(33+)离子2~2P-n~2S(2≤n≤9)的偶极跃迁行为（英文）

本文构造了高离化Kr~(33+)离子1s~2ns(2≤n≤9)和1s22p态的波函数并利用其计算了体系的非相对论能量.为了得到高精度的理论计算结果,将相对论修正和质量极化效应作为一级微扰计算了体系的总能量和2~2P-n~2S(2≤n≤9)跃迁能,本文的结果与有限的实验数据符合的较好.在此基础上完成了2~2Pn~2S(2≤n≤9)偶极跃迁三种规范下振子强度的理论计算,三者的一致性进一步证明所构造的波函数在整个空间的准确性和可靠性.     

K-doping effect of the superconductivity in K2xFeTe1-xSx (0.07≤x≤0.3)

Bulk samples of K doping K_2xFeTe_1-xS_x with x = 0.07, 0.1, 0.2, 0.3 are successfully prepared by using easy-to-use stable compound K₂S as the reactant. The lattice constant calculated from X-ray diffraction patterns indicate that K ions enter the Fe-Te-S layers. K doping is beneficial enhance the superconductivity transition temperature from the R-T curves. The apparent diamagnetic signal is observed in M-T curves when the content of K is smaller than 0.1. However, differential curves (dM/dT) in K-rich samples appear sharp slope mutations, which means that the Meissner effect signal is covered by the increased excess ferromagnetic ions. The number of excess Fe magnetic ions is proportional to K content, which may play an important role in determining the superconductivity.     

Magnetoresistance effect in A 2(FeMo)Ox double perovskites (A = Sr, Ca; 5.90≤x≤6.05)

The dependences of magnetic, electric, and magnetotransport properties on oxygen non stoichiometry were investigated in compounds of Ca₂(FeMo)O_x and Sr₂(FeMo)O_x (5.90≤x≤6.05). The regular trends in behavior of the magnetization, resistance, and magnetoresistance of samples of these series are determined. It is established that the magnetoresistance is composed of two parts that appear as a result of magnetic ordering in grain-boundary layers and of the intergrain transport of spin-polarized charge carriers. The electronic transport in the samples is assumed to be governed by percolation processes between grains which have a metallic type of conductivity and are separated by insulating spacers.     

Structure and superconductivity studies on (Y1-xLa x )Ba2Cu3O7 (0 ≤ x ≤ 1)

Studies on (Y_{1 - x}La _X )Ba₂Cu₃O₇, x = 0.0 - 1.0, in steps of 0.1, have been carried out. Results show that for x ≤ 0.4, orthorhombicity and high T_c of 90 K are retained. T_c decreases gradually for x ≥ 0.4. Pure LaBa₂Cu₃O₇ shows a T_C ^ZERO of 73 K. XRD data do not reveal any clearcut orthorhombic distortion for pure LaBa₂CuO₇ after annealing at 350°C for 4 days.     

Eu~(3+)离子激活荧光粉Ca_(1.9)Eu_(0.1)NaMg_(2-x)Zn_x(VO_4)_3(0≤x≤1)的发光性质

采用固相反应法合成了Eu~(3+)离子激活的Ca_(1.9)Eu_(0.1)NaMg_(2-x)Zn_x(VO_4)_3(0≤x≤1),并研究了其发光和热猝灭性能。经粉末X射线衍射确认,反应产物由目标相和微量杂质相EuVO_4构成。在355 nm激发下,样品中均能同时观察到来自[VO_4]_3-基团和Eu~(3+)离子的特征发光。研究结果表明:随着x值的增加,上述两种发光的强度均先增加后降低;而它们的最强激发峰位置由347 nm逐渐地红移至356 nm,Stokes位移也逐渐地减小。这种现象应归因于Zn3d轨道和O2p轨道间很强的轨道杂化效应,这种效应随着x值的增加而逐渐增强。此外,Eu~(3+)离子荧光发射强度最大值对应的x值与自激活荧光的不同。当x=1.0时,两者的相对强度差别最大。经荧光热猝灭测试确认,上述现象是由样品中的自激活荧光表现出比Eu~(3+)离子荧光更严重的荧光热猝灭造成的。因而,在紫外光激发下,样品发出荧光的颜色具有温度敏感性。     

单母体遗传算法优化(H2O)n(n≤14)的结构

在传统遗传算法的基础上提出了单母体遗传算法(single-parent genetic algorithm,SPGA),通过对母体团簇实施两种不同的变异操作对结构进行优化,给出了分子团簇结构优化的算法实现.结合TIP3P模型势函数,研究了水分子团簇(H2O)n(n≤14)的稳定结构.优化结构和已有理论及实验结果一致.计算结果表明当n＜8时,平均结合能随n,增加较快;当n≥8时有小的起伏.n=4,8,10,12的团簇结构具有较高对称性,比较稳定.     

Tin-mZrmO2n(n=2-7，0≤m≤n)团簇结构和稳定性研究

应用密度泛函理论中的B3LYP方法对Tin-mZrmO2n (n = 2-7,0≤m≤n) 团簇的基态几何结构、相对稳定性和电子结构进行了理论研究.结果表明,与桥氧链接的Ti原子被Zr原子取代后形成的混合团簇较为稳定;在团簇尺寸一定的条件下（即n相同）,随着Zr原子数m的增加,团簇的结合能基本呈线性增大,团簇的稳定性增强;Ti、Zr、O原子之间发生了电荷转移现象,形成了稳定的Ti-O-Zr键.     

电子型超导体Sm2-xCexCuO4(0.00≤x≤0.21)的异常热电势与电阻率

测量了Sm2-xCexCuO4(0.00≤x≤0.21)多晶样品的热电势S和电阻率ρ的温度依赖关系.在缘绝体-金属转变边界处,观测到热电势从绝缘体区明显的弱温度依赖关系到金属区线性温度依赖关系的转变.当Ce的含量由0.09增加到0.21时,高温下S的斜率发生由负到正的转变,这是能带的填充能级发生改变时电子型和空穴型载流子的贡献发生竞争的表现,由电子型向空穴型的过渡发生在x＝0.17处.S和ρ在200K以下的斜率变化是载流子局域化造成的.x＝0.06-0.21的样品在50K处观察到一个正的曳引峰.室温下的热电势S300K和S0(高温区热电势线性外推到0K的值)与Ce含量在绝缘体、欠掺杂和过掺杂区域有不同的依赖关系.过掺杂区域很小的S300K和S0意味着一个宽带的费米液体的贡献,同时ρ满足T2关系,二者相一致.