La＿xBi＿（2－X）Ti＿4O＿11的合成及相变研究

合成了Ｌａ＿ｘＢｉ＿（２－Ｘ）Ｔｉ＿４Ｏ＿１１系列样品，并完成了它们的喇曼光谱和ｘ射线衍射测量；结果表明，该体系在Ｘ＝１．２经历了一次相变，且相变与最低频声子模随Ｘ的变化有关。Ｌａ＿０．２Ｂｉ＿１．８·Ｔｉ＿４Ｏ＿１１的相变温度为２００℃。初步获得Ｌａ＿２Ｔｉ＿４Ｏ＿１１的结构为正交结构。     

掺杂分子晶体NH_（4－x）D_xNO_3相变中的分形行为──NO_3~－u_1、u_4振动模临界态拉曼峰强的研究

掺杂分子晶体ＮＨ＿（４－ｘ）Ｄ＿ｘＮＯ＿３相变中的分形行为──ＮＯ_３~－ｕ＿１、ｕ＿４振动模临界态拉曼峰强的研究马树国，吴国祯（清华大学物理系北京１０００８４）ＴｈｅＦｒａｃｔａｌＩｎｔｅｒｐｒｅｔａｔｉｏｎｏｆｔｈｅＰｈａｓｅＴｒａｓｉｔｉｏｎｏｆ...     

（Ba_（1－x）K_x）BiO_3芯态能级随组份的变化

本文用第一原理的ＬＤＦ－ＬＭＴＯ－ＡＳＡ方法，以超元胞Ｂａ４Ｂｉ４Ｏ（１２），（Ｂａ３Ｋ）Ｂｉ４Ｏ（１２），（ＢａＫ）Ｂｉ２Ｏ６，（ＢａＫ３）Ｂｉ４Ｏ（１２），Ｋ２Ｂｉ２Ｏ６五种“样本”计算由于Ｂｉ（＋３）和Ｂｉ（＋５）二种价态以及Ｋ掺杂引起各芯态能级化学位移的变化．“样本”的电子结构与实验相符，即Ｂａ４Ｂｉ４Ｏ（１２）是Ｅｇ＝２．０ｅＶ的半导体，（Ｂａ３Ｋ）Ｂｉ４Ｏ１２是Ｅｇ＝１．６ｅＶ其价带顶有少量空穴的半导体．其余“样本”是金属．芯态的ＬＤＦ本征值经原子模型△ＳＣＦ修正更接近实验值．用正态分布表达各芯态能级除化学位移外各种“环境因子”的影响，结合任意组份五种“样本”的伯努利分布，计算芯态电子能谱随ｘ的变化．结果表明，所有芯态的自旋一轨道分裂与实验完全相符，Ｂｉ（＋３）和Ｂｉ（＋５）二种价态引起各芯态化学位移的变化均小于０．２ｅＶ，Ｋ掺杂使各芯态结合能略有增加，其中Ｂｉ（４ｆ），Ｂａ（５ｄ）约１．３～１．５ｅＶ，其他芯态约０．４ｅＶ，以上计算结果与实验基本一致．     

R＿（1－x）Pr＿xBa＿2Cu＿3O＿（7－δ）超导T＿c平台的离子尺寸效应

系统地研究了Ｒ＿（１－ｘ）Ｐｒ＿ｘＢａ＿２Ｃｕ＿３Ｏ＿（７－δ）的超导Ｔ＿ｃ与Ｐｒ替代浓度ｘ的关系。发现在离子半径ｒ＿ｉ≤ｒ＿ｉ（Ｄｙ）时，在低Ｐｒ浓度范围内存在一个超导Ｔ＿ｃ平台，并且平台宽度表明一个Ｒ￣（３＋）离子尺寸效应。我们认为，Ｔ＿ｃ平台宽度的离子尺寸效应可能起源于Ｐｒ４ｆ电子局域态的改变。提出一个临界Ｒ￣（３＋）离子半径ｒ＿（ｉｃ），ｒ＿ｉ＞ｒ＿（ｉｃ）时ＲＢａ＿２Ｃｕ＿３Ｏ＿（７－δ）的超导电性消失     

Optical Associative Memory Based on Double Phase Conjugation Using Bi_（12）TiO_（20） Photorefractive Fi

ＯｐｔｉｃａｌＡｓｓｏｃｉａｔｉｖｅＭｅｍｏｒｙＢａｓｅｄｏｎＤｏｕｂｌｅＰｈａｓｅＣｏｎｊｕｇａｔｉｏｎＵｓｉｎｇＢｉ＿（１２）ＴｉＯ＿（２０）ＰｈｏｔｏｒｅｆｒａｃｔｉｖｅＦｉｂｅｒ￥ＬＩＵＳｈｕｔｉａｎ（ＤｅｐａｒｔｍｅｎｔｏｆＰｈｙｓｉｃｓ，...     

（Ba_1－_xK_x）BiO_3电子结构与超导电性

用第一原理的ＬＤＦＬＭＴＯＡＳＡ超元胞法，模拟由Ｘ射线吸收谱精细结构测定的ＢａＢｉＯ３中，Ｂｉ有两种价态Ｂｉ３＋和Ｂｉ５＋及与之相应的两种不同键长的Ｂｉ—Ｏ八面体，以及Ｋ掺杂对晶体结构的影响．计算了Ｂａ４Ｂｉ４Ｏ１２，（Ｂａ３Ｋ）Ｂｉ４Ｏ１２，（ＢａＫ）Ｂｉ２Ｏ６，（ＢａＫ３）Ｂｉ４Ｏ１２，Ｋ２Ｂｉ２Ｏ６（简记为（４０４），（３１４），（１１２），（１３４），（０２２））五种“样本”的电子结构．结果表明，（４０４）和（３１４）分别为Ｅｇ＝１６ｅＶ及Ｅｇ＝１５ｅＶ的半导体，其它“样本”为金属．总能的分析表明（１３４）是不稳定的，故溶解极限为ｘ＝０５．以“取样”方式按伯努利分布确定任意组分各“样本”的概率，进而计算了（Ｂａ１－ｘＫｘ）ＢｉＯ３电子结构随组分的变化．最后用逾渗模型说明了超导转变温度Ｔｃ在ｘ＝０．２５附近的突变     

（Ba1—xKx）BiO3芯态能级随组份的变化

本用第一原理的ＬＤＦ－ＬＭＴＯ－ＡＳＡ方法，以超元胞Ｂａ４Ｂｉ４Ｏ１２，（Ｂａ３Ｋ）ＢｉＯ１２，（ＢａＫ）Ｂｉ２Ｏ６，（ＢａＫ３）Ｂｉ４Ｏ１２，Ｋ２Ｂｉ２Ｏ６五种“样本”计算由于Ｂｉ＾＋３和Ｂｉ＾＋５二种价态以及Ｋ掺杂引起各芯态能级化学位移的变化，“样本”的电子结构与实验相符，即Ｂａ４Ｂｉ４Ｏ１２是ｇ＝－２．０ｅＶ的半导体，（Ｂａ３Ｋ）Ｂｉ４Ｏ１２ｊ Ｅｇ＝１．６ｅＶ其价带顶有不量空穴的半导体，     

Fe（Ⅲ）、Al（Ⅲ）、Ni（Ⅱ）非有机溶剂液－液萃取行为的研究

本文研究了ＰＥＧ（聚乙二醇）－２０００－钍试剂－（ＮＨ＿４）＿２ＳＯ＿４体系对Ｆｅ（Ⅲ）、Ａｌ（Ⅲ）、Ｎｉ（Ⅱ）的非有机溶剂萃取行为。指出在ｐＨ为３．５－６．５（ＮａＡｃ－ＨＡｃ）的水溶液中，有（ＮＨ＿４）＿２ＳＯ＿４存在下，Ｆｅ（Ⅲ）、Ａｌ（Ⅲ）可被ＰＥＧ－２０００相几乎完全萃取，而Ｎｉ（Ⅱ）则基本上不被萃取。从而获得了Ｎｉ（Ⅱ）与Ｆｅ（Ⅲ）、Ａｌ（Ⅲ）混合离子的定量分离。     

非晶态（Fe＿（1－x）Co＿x）＿（77．5）Nd＿4B＿（18．5）合金的电阻率的压力系数和压力弛豫研究

在０．０００１－２．４ＧＰａ流体静压力范围详细研究了非晶（Ｆｅ＿ｘＣｏ＿ｘ）＿（７７．５）Ｎｄ＿４Ｂ＿（１８．５）（０≤ｘ≤１．０）合金的电阻率与压力的关系，得到该非晶合金电阻率的压力系数随组分ｘ变化的规律。结果表明：用少量的钴（ｘ＝０．２）替代铁，不会影响其硬磁性和热稳定性，同时却可减小电阻率的压力系数，从而增强电磁性能在压力下的稳定性。此外还观测到在０．５１ＧＰａ保压３－２４ｂ的结构弛豫，进一步求出该非晶台金电阻率的压力弛豫时间对组分ｘ的依赖关系。     

ZnO－Bi＿（2）O＿（3）－Sb＿（2）O＿（3）－BaO系陶瓷的晶界相与抗退降性能

在通常的ＺｎＯ－Ｂｉ＿２Ｏ＿３－Ｓｂ＿２Ｏ＿３系电压敏陶瓷中，加入能构成压敏特性的钡添加剂，发现除已知的Ｂｉ＿２Ｏ＿３和Ｚｎ＿２．３３Ｓｂ＿０．６７Ｏ＿４晶界相以外，还出现新的晶界相，分析表明是固溶有微量其它成分的偏锑酸钡（ＢａＳｂ＿２Ｏ＿６）晶相。同时还发现，ＢａＳｂ＿２Ｏ＿６相是热稳定的，它对改善压敏陶瓷的退降性能起重要作用。通过控制各种添加剂的含量，使晶界相Ｂｉ＿２Ｏ＿３，Ｚｎ＿２．３３Ｓｂ＿０．６７Ｏ＿４和ＢａＳｂ＿２Ｏ＿６之间的数量有适当比例时，压敏陶瓷在长期电负荷作用下和脉冲大电流作用下的抗退降能力都有显著的提高，特别可贵的是反向Ｖ—Ｉ特性的退阵有很大的改善。     

Effect of trivalent iron substitution on structure and properties of PLZT ceramics

Polycrystalline samples of Fe-modified PLZT (lead lanthanum zirconate titanate) are prepared by a mixed-oxide reaction technique. The formation of the compound has been confirmed by X-ray powder diffraction studies. The unit cell structure of the material has been found to be rhombohedral. Fourier-transform infrared reflection (FTIR) spectra have been recorded to correspond the structural changes associated with the phase formation. The effects of Fe concentration on the microstructure and dielectric constant of PLZT materials have been investigated. The ferroelectric phase transition of PLFZT materials is studied using dielectric measurements, which shows a shift in the transition temperature towards the higher-temperature side with increased Fe ion concentration. The piezoelectric constants of this system are investigated by the same way of changed contents of Fe ion in the main PLZT compound. The optimum values of Q_m, k_p, and d₃₃ are 73, 0.32 and 406. The electrical conductivity increases with the increase in Fe ion concentration. PACS 77.80.Bh; 77.84.Dy; 77.22.Ch; 72.15.Eb; 06.60.Ei; 39.30.+w     

A New Fluorescent Sensor for the Determination of Iron(III) in Semi-Aqueous Solution

A simple fluorescent sensor 1 has been developed for the recognition of Fe(III) in semi-aqueous solution at pH 7.0. The sensor, containing two Schiff base type receptors directly connected to naphthalene fluorophores, shows a concentration dependent decrease in emission intensity upon Fe(III) addition. The sensor was selective for Fe(III) over other metal ions and can measure Fe(III) ion concentration between 0.05 and 0.12 mM. The binding stoichiometry was established as 1:1 (host: guest) with a binding constant (Logβ) of 4.01. Furthermore, the addition of Fe(III) to a solution of 1 caused a colour change from light yellow to colourless meaning 1 is also capable of detecting Fe(III) by the naked eye.     

Initial oxidation stages on FeCr(100) and FeCr(110) surfaces

Simultaneous LEED and AES are used to follow early stages of oxidation of monocrystalline FeCr(100) and (110) between 700 and 900 K in the oxygen pressure range 10^?9–10^?6 Torr. A chromium-rich oxide region at the alloy/oxide interface is observed, which exhibits different surface structures on oxidized FeCr(100) and FeCr(110). The chromium concentration in this initially formed oxide film is found to be enhanced by low oxygen pressures or high temperatures. During further oxidation different behaviours are observed on FeCr(100) and FeCr(110), which are explained by assuming different ion permeabilities through the initial chromium rich oxide regions on the two surface planes. On FeCr(110) surfaces oxidation is initiated on chromium enriched (100) facets at 800 K or below. At 900 K a film consisting of rhombohedral Cr₂O₃ or (Fe, Cr)₂O₃ is epitaxially growing with its (001) plane parallel to the alloy (110) face. On FeCr(100) surfaces the chromium rich oxide region next to the substrate is of fcc type. As soon as the diffusion of iron from the alloy to the gas/oxide interface is observable, a spinel type oxide is formed and connected with the location of iron in tetrahedral lattice sites. Closer to the fcc lattice the spinel oxide consists of FeCr₂O₄ or a solid solution of FeCr₂O₄ and Fe₃O₄ whereas next to the gas phase the oxide is pure Fe₃O₄.     

铁(Ⅱ,Ⅲ)对邻苯二甲酸铕(Ⅲ)荧光性能的猝灭研究

在液相中合成了掺杂不同浓度Fe2 ,Fe3 的邻苯二甲酸铕系列配合物,测定了该系列配合物的荧光光谱和红外光谱.实验结果表明,微量Fe2 ,Fe3 的存在对邻苯二甲酸铕荧光产生了猝灭作用.这可能是由于配合物在发光过程中Fe2 捕获了基态的空穴或者Fe3 捕获了激发态的电子所引起的.     

Direct observation of charge transfer in double-perovskite-like RbMn[Fe(CN)6

The charge density distribution has been determined for a transition metal cyanide, RbMn[Fe(CN)(6)], by means of the maximum entropy-Rietveld method combined with the highly angularly resolved synchrotron radiation x-ray powder diffraction at SPring-8 BL02B2. We directly observed a charge transfer from the Mn site to the Fe site in the low-temperature phase. On the basis of a local density approximation calculation, we discuss the origin for the anisotropic bonding electron distribution around the Mn3+ ion in the low-temperature phase.     

Structure, spin reorientation and M(o)ssbauer effect studies of Tb0.3Dy0.7(Fe1-xAlx)1.95 alloys

The effect of Al substitution for Fe on crystal structure, magnetostriction and spontaneous magnetostriction, anisotropy and spin reorientation of a series of polycrystalline Tb0.3Dy0.7(Fe1-xAlx)1.95 alloys (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25, 0.30, 0.35) at room temperature and 77 K was investigated systematically. It was found that the primary phase of Tb0.3Dy0.7(Fe1-xAlx)1.95 is the MgCu2-type cubic Laves phase structure when x < 0.4 and the lattice constant a of Tb0.3Dy0.7(Fe1-xAlx)1.95 increases approximately and monotonically with the increase of x. The substitution of Al leads to the fact that the magnetostriction ( inceases slightly in a low magnetic field (H ≤ 40 kA/m), but decreases sharply and is easily close to saturation in a high applied field as x increases, showing that a small amount of Al substitution is beneficial to a decrease in the magnetocrystalline anisotropy. It was also found that the spontaneous magnetostriction (ζ)111 decreases greatly with x increasing. The analysis of the M(o)ssbauer spectra indicated that the easy magnetization direction in the {110} plane deviates slightly from the main axis of symmetry with the changes of composition and temperature, namely spin reorientation. A small amount of non-magnetic phase exists for x = 0.15 in Tb0.3Dy0.7(Fe1-xAlx)1.95 alloys and the alloys become paramagnetic for x > 0.15 at room temperture, but at 77 K the alloys still remain magnetic phase even for x = 0.2. At room temperature and 77 K, the hyperfine field decreases and the isomer shifts increase with Al concentration increasing.     

Ultraviolet photoelectron studies of the chemisorption and decomposition of propyne on Fe(110) and Fe(100) surfaces

The chemisorption and decomposition of propyne on clean Fe(110) and Fe(100) surfaces have been studied by ultraviolet photoelectron spectroscopy (UPS). The UPS spectra suggest that exposure at 78 K produces chemisorbed propyne on both these surfaces, while excess exposure of the adsorbate produces a condensed propyne phase at the same temperature. Upon warming to ～100 K, the condensed phase disappears and the chemisorbed phase appears again on both the surfaces. Further warming to ～170 K produces a dissociatively adsorbed propyne phase on Fe(100), and the spectral features then scarcely change for further warming to ～370 K. In the case of Fe(110), on the other hand, the chemisorbed phase is apparently unchanged by heating even up to ～370 K. All peaks due to chemisorbed propyne on both Fe(110) and Fe(100) disappear at ～470 K, with the formation of carbonated surfaces.     

EPR of the first Fe(III)-containing spin-crossover metallomesogens

The low-spin (LS) to high-spin (HS) transition in two mesogenic Fe(III) complexes with alkyloxysalicyliden-N^′-ethyl-N-ethylendiamine as ligands is studied by electron paramagnetic resonance (EPR). The symmetrization of the crystal field around the Fe(III) ion under first heating of a polycrystalline sample from the room temperature was observed in the spectra of HS complexes. The line narrowing (from 45 to 15 mT) under the crystal-smectic phase transition is explained by the strengthening of the intermolecular exchange interaction, as a result of the structural reorganization of layers in the smectic phase. A feature of both mesogenic spin-transition systemsis an unusual field-induced spin instability which leads to the hysteresis of the HS-LS composition. This instability is detected by EPR and magnetic susceptibility methods. The alignment of systems by magnetic field in the mesophase and a complete or partial orientational order under cooling the mesophase to the glass state are the main reason for this hysteresis. The influence of EPR-silent LS complexes reveals itself in the line broadening of HS compounds’ when the temperature is lowered from 220 K.     

Investigation of magnetic properties in 57Fe/Al multilayers

Fe/Al multilayer thin films prepared by ion beam sputtering, with an overall atomic concentration ratio of Fe/Al = 1:2 have been studied by x-ray diffraction spectroscopy (XRD), X-ray reflectivity (XRR) and D.C. Magnetization. These studies show the formation of Fe–Al intermetallic layers. Two magnetic regions and transition temperatures of 473 and 533 K are evident from magnetization studies. Conversion Electron Mössbauer Spectroscopy (CEMS) shows formation of off-stoichiometric Fe₃Al like phase and phases consisting of pure Fe and Fe-rich extended Fe–Al solutions.     

光度法研究聚乙二醇-硫酸铵-邻苯三酚红体系中铋(Ⅲ), 铁(Ⅲ), 铜(Ⅱ), 镍(Ⅱ), 钴(Ⅱ), 铅(Ⅱ)的萃取分离

本文研究了在聚乙二醇(PEG)-硫酸铵[(NH_4)_2SO_4]-邻苯三酚红(PR)体系中Bi(Ⅲ),Fe(Ⅲ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Pb(Ⅱ)的萃取行为。实验结果表明,Bi(Ⅲ)在pH3.5～6.5及Fe(Ⅲ)在pH4.0～7.0范围内可以被PEG相几乎完全萃取,而Cu(Ⅱ),Co(Ⅱ)在pH1.0～7.0,Pb(Ⅱ)在pH2.0～7.0,Ni(Ⅱ)在pH1.0～4.5则不被萃取。从而实现了将Bi(Ⅲ)(pH3.5),Fe(Ⅲ)(pH5.0)与Cu(Ⅱ),Co(Ⅱ),Pb(Ⅱ),Ni(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。