求解非中心对称晶体结构的人工相位退化法

在用直接法推引非中心对称晶体结构因子的相位时,如果人为地使相位退化为实分量的正负号,可以获得同时包含真实结构及其对映体的E图。利用分量关系式不难使这样的E图复原,从而解出结构。这样做,对于每一个参加相位排列的起始衍射只需考虑两种可能的相位值(0或π),因而比通常的相位排列法节省计算量。 关键词：     

GaSe：AgGaSe_2晶体的光学性能及应用（英文）

从GaSe∶AgGaSe₂熔体(质量掺杂浓度为10%)中生长的非线性光学晶体ε-GaSe∶Ag晶体(质量掺杂浓度≤0.04%)是一种非中心对称晶体,可用于相位匹配频率转换。Ag的掺入使GaSe晶体的显微硬度提高了30%,从而使其可以在任意方向上进行切割和抛光。本文研究了GaSe∶AgGaSe₂晶体在可见、中红外及太赫兹波段的光学性能。实验证明:GaSe∶AgGaSe₂晶体的吸收系数是纯GaSe晶体的2倍,其CO₂激光倍频效率是ZnGeP₂晶体的1.7倍。     

YFeO3的电子结构和光学性质的第一性原理研究

稀土正铁氧体YFeO₃呈正交钙钛矿结构,其晶体和纳米晶材料在电极材料、 传感器和光催化领域具有重要的应用价值.用平面波赝势方法,采用广义梯度近似、改进的Perdew-Burke-Emzerhof交换-关联势、 实空间超软赝势计算方案,研究了YFeO₃晶体的几何结构、电子结构和光学性质. 计算得到的晶格参量与报道的实验结果一致.通过对能带结构、态密度、介电函数、吸收系数和光电导率的计算和分析, 确定YFeO₃是直接能隙半导体,能隙E_g约为2.22 eV,阐明了YFeO₃晶体和纳米晶具有较好的可见光催化性能.     

异垂盆草甙元晶体结构的测定(Ⅱ) 用分量关系式复原对映双解E图

以附加记号法测定异垂盆草甙元的晶体结构时,出现了相位退化问题,由此得到同时混含两个对映体的E图,应用分量关系式成功地将这样的E图复原为只含一个对映体的E图。这一成功表明:使用附加记号法测定非中心对称的晶体结构,当出现相位退化时无需迴避,这就提高了附加记号法的使用效力。     

异垂盆草甙元晶体结构的测定(Ⅱ)——用分量关系式复原对映双解E图

以附加记号法测定异垂盆草甙元的晶体结构时,出现了相位退化问题,由此得到同时混含两个对映体的E图,应用分量关系式成功地将这样的E图复原为只含一个对映体的E图。这一成功表明:使用附加记号法测定非中心对称的晶体结构,当出现相位退化时无需迴避,这就提高了附加记号法的使用效力。     

产生蓝色相干辐射和实现Nd:YAG 1.0642μm倍频90°非临界相位匹配的Nb:KTiPO4

本文报道了用熔盐顶部籽晶法生长Nb浓度(0～13)mol%的Nb:KTP晶体的倍频的Ⅱ型相位匹配的截止波长和Nd:YAG1.0642μm及Nd:YA1O₃1.0795μm激光在这些晶体中倍频的最佳相位匹配角的测量结果.从中可看出,由于Nb⁵⁺的引入使KTP晶体倍频的Ⅱ相位匹配的截止波长有效蓝移,目前已使截止波长蓝移至937nm且有效产生468.5nm的倍频蓝光.同时Nb⁵⁺的引入使Nd:YAG1.0642μm激光和Nd:YA1O₃倍频的最佳相位匹配方向产生很大的变化,目前已使Nb:KTP晶体倍频的最佳相位匹配方向为θ=88.32°、Φ=0°,非常接近于90°非临界相位匹配方向.     

掺锌LiNbO3晶体的生长及其光学性能

在LiNbO₃中掺进3mol%、5mol%、7mol%ZnO生长Zn:LiNbO₃晶体.测试Zn:LiNbO₃晶体的吸收光谱,研究Zn:LiNbO₃晶体吸收边紫移的机制.测试Zn:LiNbO₃晶体的红外光谱,研究Zn(7mol%):LiNbO₃晶体OH 吸收峰由3484cm^-1移到3530cm^-1的机制.测试Zn:LiNbO₃晶体倍频转换效率和相位匹配温度,研究Zn:LiNbO₃晶体倍频转换效率增强的机制.     

In掺杂ZnO电子结构的第一性原理研究

采用第一性原理平面波超软赝势,计算了纤锌矿ZnO和不同掺杂量下In掺杂ZnO晶体的能带结构、态密度和分波态密度.计算表明,In的掺杂导致ZnO禁带宽度变窄.随着掺杂量的增大,In_xZn_1－xO的导带底和价带顶同时下降,但是导带底比价带顶下降得多,这导致了带隙的变窄.此外,In掺杂使晶胞晶格常数增大,这对带隙的变窄也有一定作用.     

二元固溶体的配分函数

这篇论文是作者之一的某一篇论文的继续。论文分四节。在第一节中我们讨论的对象是应用二元混合气体的买厄理论至一个在AB型晶体上的二元固溶体而获得的不可约集团积分B(v₁,v₂)。我们严格地证明了它们是某一些晶体常数z₁,z₂,…的线性函数。这些常数的定义为1/((1/2)N)∑λ_abλ_a′b′…,式中N代表晶点阵的点的总数,λ_ab为邻矩阵,定义为λ_ab=1 如果ab为近邻, =0,如果ab不是近邻, a,a′,…互不相等,b,b′,…也互不相等,而乘积λ_ab…为全部下标的一个不可约乘积。证明共用了三个定理,同时也援用了一个所谓基本不可约集团的定义。在第二节中,我们应用了第一节的讨论对B(2,3)作了计算。在第三节中,我们应用第一节的结果,简化了求固溶体自由能的Kirkwood方法,同时也利用了简化的方法求得了自由能对(kT)^-1展开的幂级数中(kT)^-7的系数。比(kT)^-7更早的项的系数早已在作者之一的一篇论文中求得。在第四节中,我们利用第一节的结果,证明了严格理论在忽略z₂,z₃,…时即成了Bethe理论的第一级近似。如果将自由能表为z₁,z₂,…的函数而称它们的系数为f₁,f₂,…,那末我们指出:只消研究在某些赝点阵上的固溶体的配分函数,便可以求出f₁,f₂,…,同时我们也指出:在这些赝点阵上的固溶体的配分函数是可以(而也容易)严格地求出的,因此以上的理论供给了我们一个较好的求固液体的自由能的方法。     

Ce掺杂SrMnO3的电子结构和磁性的第一性原理研究

用含超软赝势平面波方法的广义梯度近似第一性原理对Ce掺杂SrMnO₃的电子结构和磁性进行了相关研究. 不同的Mn-O键长说明MnO₆八面体发生了强的Jahn-Teller扭曲, 并伴随着晶体构型由立方体(Pm3m)转变为四方晶系(I4/mcm), 同时,Jahn-Teller扭曲也稳定了C型反铁磁基态构型. 电子结构结果表明SrMnO₃和Sr_1-xCe_xMnO₃(x=0.12     

Local atomic structure of niobates and titanates from X-ray absorption spectroscopic data

The local atomic structure of PbTiO₃, BaTiO₃, and KNbO₃ perovskite-type crystals and K _x Na_{1 ? x} NbO₃ solid solutions in different phases is investigated using the angular dependence of the pre-edge structure of the Ti and Nb K X-ray absorption spectra and the EXAFS data. In noncubic phases, a considerable deviation of the local structure from the structure determined from diffraction data is observed only for the tetragonal phase of the BaTiO₃ crystal. It is revealed that, in the cubic phase of niobates, the niobium atoms are characterized by significant displacements from the centrosymmetric positions along the threefold axes, so that they are close in the magnitude and the direction to the displacements in the low-temperatures rhombohedral phases.     

Phase transitions in 3,5-dichloropyridine

Abstract

Structural phase transitions in 3,5-dichloropyridine crystal have been studied by calorimetry (150–300 K), X-ray diffraction (300 K), ³⁵Cland ¹⁴N nuclear quadrupole resonance (75–300 K) and vibrational spectroscopy (20–300K). Three phases have been shown to exist: phase I, between 338 and 287.5 K, phase 11, between 287.5 and 167.5 K, and phase 111, below 167.5 K. Phase I is characterised by the space group P 2,/m and Z = 2 whereas phases I1 and 111 remain centrosymmetric but double the unit cell. All the phases are ordered and contain crystallo- graphically equivalent molecules. The I ? I1 transition is of first order and probably of the reconstructive type while the II ? III transition is believed to be displacive. Both transitions are monitored by predominantly R′_x and R′_z librational motions.     

Overall values of conventional discrepancy indices for related and unrelated models of a non-centrosymmetric crystal with a centrosymmetric group

Theoretical expressions for the overall values of the conventional discrepancy indicesR(F) andR(I) are derived for a non-centrosymmetric crystal with a centrosymmetric group by taking the centrosymmetric group and a part of the other atoms in the unit cell as the trial structure. These results are used to obtain tables of values of these indices in terms of the parameter σ _1c ² and σ ₁ ² which define the fractional contribution to the local mean intensity from the centrosymmetric group and all the known atoms respectively. Contribution No. 561     

Polarized Raman spectra of brushite (CaHPO4.2H2O) crystal. Investigation of the phosphate stretching modes,study of the LOTO splitting

Polarized Raman measurements were recorded on a monoclinic brushite (CaHPO₄.2H₂O) crystal in the 800–1200 cm⁻¹ spectral range, corresponding to the P O stretching modes. This study is a continuation of the investigation of the phosphate stretching modes observed in polarized infrared reflectance spectra of brushite crystal. In such ionic non‐centrosymmetric crystals, the splitting between the transverse and longitudinal components of the optic vibrations was observed in the polarized Raman spectra recorded at several scattering geometries. A″ symmetry modes of the brushite crystal were measured. Using a simple model based on the symmetry of the PO₄ group, the Raman intensities of the stretching modes are calculated and compared with experimental bands. Copyright © 2016 John Wiley & Sons, Ltd.     

Growth of ZnInGaS4 by normal freezing method

The crystal structure and phase transition of ZnInGaS₄ were described. The ZnInGaS₄ had both a defect chalcopyrite and a layered structure below 920 °C, and only the layered structure ZnInGaS₄ existed between 920 and 1020 °C. The layered structure ZnInGaS₄ was grown using the normal freezing method. The bandgap of the layered structure ZnInGaS₄ was estimated to be approximately 2.6 eV and it is possibly a direct bandgap. This is a first step toward realizing the novel functions of ZnInGaS₄.     

Neutron-diffraction study of the crystal structure of BaTiO<Subscript>3</Subscript> ferroelectric doped with iron

The crystal structure of iron-doped barium titanate BaTi_1–x Fe _x O₃ is studied by neutron diffraction in the range of 0 ≤ x ≤ 0.12. At low concentrations of iron, x < 0.01, and at room temperature, these compounds have a polar structure with tetragonal symmetry with space group P4mm. The temperature of the transition of the tetragonal ferroelectric phase into the cubic paraelectric phase with space group Pm \(\bar 3\) m for an iron concentration of x = 0.01 is 390 K (for pure BaTiO₃, it is 410 K). At an iron concentration of x = 0.07, the crystal structure of the studied compounds varies, and it is described by the centrosymmetric hexagonal space group P6₃/mmc. The structural parameters of various phases of compound BaTi_1–x Fe _x O₃ are determined from the experimental data.     

Direct experimental method for the determination of x-ray reflection phases

A direct experimental method is described for the phase determination of x-ray reflections from single crystals. This method utilizes the coherent dynamical interaction of diffracted x-ray beams in a 3-beam multiple Bragg reflection to reveal the signs,S _P, of triplet-phase products. This dynamical effect and the relative rotation of the crystal lattice with respect to the Ewald sphere are considered. The phase dependence of the reflected intensity profile is observed and is in agreement with the theory. It is found thatS _P=S _L ·S _R,S _L being the sign defined from the multiple diffraction line profile.S _R is determined by the rotation of the crystal lattice relative to the Ewald sphere. The new method can be applied to a direct experimental determination of phases without carrying out the complicated dynamical calculations.On leave from Instituto de Fisica, Universidade Estadual de Campinas, Campinas, S.P. 13100, Brazil     

Novel pyridyl‐substituted coumarin and its perchlorate salt–crystal structure and spectroscopic properties

The novel pyridyl‐substituted coumarin ( 1 ) and its perchlorate salt ( 2 ) have been synthesized and their structure and properties elucidated in detail spectroscopically, thermally and structurally, using single crystal X‐ray diffraction for 2 , linear‐polarized solid state IR‐spectroscopy, UV‐spectroscopy, TGA, DSC, DTA, and positive and negative ESI MS. Quantum chemical calculations were used to obtain the electronic structure, vibrational data and electronic spectra. The studied compound crystallizes in the centrosymmetric space group P‐1 and exhibits an infinite layered structure with the ions linked by means of the intermolecular N⁺H…OClO₃ (2.795 Å) interactions. The cations are disposed in a manner leading to a significant π‐stacking effect with a distance of 2.980 Å. The effects of N_py protonation on the optical and magnetic properties are elucidated by comparing the data of the protonated and neutral compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Carbon monoxide adsorption kinetics on molybdenum (100)

In an ultrahigh vacuum system (10^?10 torr) LEED, Auger spectroscopy, flash desorption and work-function measurements have been used to follow the kinetics of adsorption of carbon monoxide on the (100) face of a molybdenum single crystal. At room tempeiature CO adsorbs into three β states β₁, β₂, β₃, which are associated with different work-function changes: the phase β₃ is found to correspond to a decrease of work-function whereas the phases β₁ and β₂ correspond to an increase. The total change of surface potential is about 0.50 eV at saturation. An ordered C (2×2) structure is found for the β₂ + β₃ phases, and is associated at their maximum coverage (about half a monolayer) with a work-function change of + 0.070 eV with respect to the clean surface. At completion of the monolayer a P (1×1) structure is observed.     

Calculations of physical properties of pure and doped crystals: Ab initio and semi-empirical methods in application to YAlO3:Ce and TiO2

In this paper we demonstrate that two independent methods of calculations (DFT based ab initio and semi-empirical crystal field theory) can be used to form a complementary picture of the optical and electronic properties of the doped host and impurity ion. The crystals considered in the present paper are: (i) YAlO₃:Ce³⁺ and (ii) two dominant phases of TiO₂—rutile and anatase. As an example, detailed calculations of the band structure and crystal field energy level scheme of YAlO₃:Ce³⁺ are reported. From the analysis of the band structure and density of states, the character of the YAlO₃ energetic bands and positions of the Ce impurity energy levels were established. It was also shown how the ab initio methods can be used for calculations of the structural properties of solids under elevated pressure. Taking the two dominant phases of TiO₂ as an example, it was demonstrated how the elastic properties can be extracted from the calculated unit cell’s volume at different pressures. Particular attention was paid to the microscopic effects of crystal field, which were evidenced by the pressure-induced changes of the structure and shape of distribution of the Ti 3d electrons density of states. It was demonstrated how the difference in crystal structure of the anatase and rutile phases leads to remarkable difference in microscopic crystal field effects, which was explained by different Ti-O distances in both phases. In addition, the pressure dependence of the band gaps for anatase and rutile was investigated. It was shown that the hydrostatic pressure leads to the band gap narrowing in anatase and band gap widening in rutile, with pressure coefficients +0.00681 eV/GPa for rutile and −0.0088 eV/GPa for anatase.