共生晶体Mn2Hg4(SCN)12和MnHg(SCN)4的形成

采用恒温蒸发法从水溶液中生长Hg2+、Mn2+为双配位中心的SCN- 的配合物晶体.生长液中Hg2+含量较SCN-适当过量的条件下,出现Mn2Hg4(SCN)12晶体和MnHg(SCN)4晶体共生现象.MnHg (SCN)4晶体中Hg2+只与SCN-配位,Mn2+只与NCS-配位,而Mn2Hg4(SCN)12晶体中部分Hg2+可以同时与SCN-和NCS-配位体结合,并且部分SCN-同时和2个Hg2+结合成桥式结构.Mn2Hg4(SCN)12晶体中Mn2+的配位数由MnHg(SCN)4晶体中的4配位增大为5配位和6配位.Mn(NCS)4-6 和Mn(NCS)3-5 配位多面体的存在使Mn2Hg4(SCN)12晶体的颜色比MnHg(SCN)4晶体的颜色浅.     

掺Nd钒酸盐晶体热导率的拉曼光谱研究

运用晶格动力学观点推导了热导率与积分拉曼散射强度的关系,测量了Nd:YVO4 (简称NYV)和Nd:GdVO4 (简称NGV)不同配置下的高温拉曼光谱和其a、c向的热导率,理论与实验非常吻合.     

配合物晶体MnHg(SCN)4的晶形分析

配合物晶体MnHg(SCN)4中维系晶体结构的化学键是-Mn-NCS-配位键.从MnHg(SCN)4晶体中配位键的分布特点出发,对属于点群4的单形四方四面体、四方柱和平行双面进行分析,确定晶形中不能出现平行双面{001}、四方柱{110},可以出现的单形为四方四面体{101}和{011}及四方柱{100},而且四方四面体{101}和{011}单形最发育.由结构分析得出的晶形特点与实际晶体晶形特点相符.     

二维类三角晶格声子晶体的声学带隙特性分析

首先划分7种类三角晶格声子晶体按三角点阵排列,并推导它们的结构因子,然后利用平面波展开法数值计算了类三角晶格水/水银声子晶体的能带结构,分析了带隙的各向同性以及归一化半径对带隙的影响.结果表明:(3.4.6.4)品格、(34.6)晶格、(3.6.3.6)晶格、(63)晶格水/水银声子晶体可以产生较宽频率范围的带隙;(3.12.12)晶格和(4.6.12)品格水/水银声子晶体存在很窄低频带隙;单胞含6个和3个“原子”水/水银声子晶体容易形成各向同性带隙;选取归一化半径分别为0.38和0.28,使类三角晶格水/水银声子晶体的第1和第2带隙都获得最大值.     

GaN体单晶的氨热生长及应力调控

采用氨热法在碱性条件下生长了GaN体单晶,SEM照片显示晶体表面有大量裂纹.用拉曼光谱测量GaN晶体的E2 (high)声子拉曼峰,结果表明晶体内部应力波动较大.通过减小温度梯度、籽晶优选及降温程序优化后,得到了无裂纹的氮化镓晶体,(002)和(102)的X射线摇摆曲线FWHM分别为48 arcsec和54 arcsec,显微拉曼光谱表明经过工艺优化后的晶体应力显著降低,应力的来源主要为生长过程中杂质的引入.     

Ga3PO7晶体的非弹性振动特性

采用拉曼散射技术,从声子角度研究了Ga3PO7晶体的非弹性振动特性,主要内容为:采用位置对称性法从理论上计算了晶体的晶格振动模式,判定了晶体共有27个拉曼活性模,其振动模式为Γ=7Al+10E,可看作由PO43-集团形成的晶体的内振动模和由PO43-集团、O和Ga原子形成的晶体的外振动模组成;通过室温拉曼光谱实验观测到了晶体的16个拉曼活性模,包括8个外振动模和6个内振动模,并对各模进行了指认,其中高波段的声子模主要为PO4四面体的内振动模.由于晶体结构缺陷和某些内、外振动模的耦合等原因,观测到的振动模数量明显少于理论预测值.     

ZCSC和CMSC晶体热学性质的理论研究

采用密度泛函理论计算了ZnCd(SeCN)4(简称ZCSC)和CdHg(SeCN)4(简称CMSC)晶体的声子色散谱、声子态密度,系统研究了这两种晶体的比热容、热膨胀率、热导率、热扩散率等热学性质.理论计算得到常温下ZCSC和CMSC晶体的比热容分别为0.454 J·g-1·K-1和0.374 J·g-1·K-1,而本文通过差示扫描量热仪实验测量这两种晶体的比热容分别为0.460 J·g-1·K-1和0.306 J·g-1·K-1,理论计算与实验结果相符.研究结果还表明ZCSC晶体的热导率及热扩散率均为CMSC晶体的5～7倍,而ZCSC晶体的热膨胀率约是CMSC晶体的1/3,因此ZCSC晶体是热学性质优异抗激光损伤能力强的非线性光学晶体.     

LaxFe3CoSb12多晶材料的制备和拉曼光谱测定

用熔融退火法制备了镧填充方钴矿(LaxFe3CoSb12)多晶热电材料.用背散射方法测定了不同掺镧量晶体的拉曼光谱.我们认为晶格孔隙中镧原子的振颤运动产生了有效的声子散射并使拉曼谱线加宽.随着镧含量的增加,镧原子振颤自由度降低,谱线的加宽程度减少.     

含钡硫铝酸钙晶体的合成及其结构和形态

以CaCO3,Al2O3,BaSO4和CaSO4*2H2O为原料,在1350℃加热合成C(4-x)BxA3粉晶,然后以PbCl2为助熔剂,借助于熔盐法制备了含钡硫铝酸钙单晶,在对其粉晶X射线多晶衍射谱指标化的基础上,以高纯Si作内标测定了C(4-x)BxA3(x=0.25,0.5,0.75,1.00)晶体属等轴晶系,立方体心晶格,晶胞参数分别为a0=9.280, 9.233, 9.261和9.303nm,与其成分变化成直线关系,符合Vegard定律.电镜观察该晶体外形为菱形十二面体.并分析了该晶体的红外光谱,认为在该晶体中存在着[AlO4]四面体.     

Ba3(VO4)2晶体的生长和拉曼性质的研究

采用提拉法生长了尺寸为φ22mm×50 mm的Ba3(VO4):晶体.室温下测试了Ba3(VO4)2晶体不同激发配置下自发拉曼散射光谱.另外测试了该晶体在532 nm、25 ps脉冲下的受激拉曼散射,观察到3阶斯托克斯线(625.5 am)和1阶反斯托克斯线(506.8 nm),并估算了Ba3(VO4)2晶体的稳态拉曼增益系数.     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

Sol-gel synthesis and characterization of adsorbent and photoluminescent nanocomposites of starch and silica

Using sol-gel method, mesoporous and photoluminescent silica nanocomposites of soluble starch have been synthesized and characterized. Different ratios of H₂O, TEOS and EtOH were used at fixed template (soluble starch) and catalyst (NH₄OH) concentrations to obtain materials of different performances in terms of heavy metal binding from a solution which has been monitored using Cd(II) as representative divalent heavy metal ion. Optimum material was obtained when H₂O, TEOS and EtOH were used in 14:1:2 ratio. This sample was not only an efficient metal ion adsorbent but also had an intense luminescence in ultra-violet region and potentially may be used in silicon-based UV-emitting devices. Metal binding by the material was further enhanced after calcination (at 800 °C in air) while its luminescence had a multipeak profile in UV-visible region. In a batch adsorption study, calcined hybrid composite (0.25 g/L) could remove 98.5% Cd(II) from 100 mg/L Cd(II) solution in 2 h. The chemical, structural and textural characteristics of the synthesized materials have been investigated using Fourier Transform Infrared Spectroscopy (FTIR), X-rays Diffraction (XRD), Thermal Analysis (TGA/DTA), Photoluminescence (PL), Brunauer-Emmett-Teller Analysis (BET) and Scanning Electron Microscopy (SEM).     

晶体中负离子配位多面体结晶方位、形变与晶体压电、铁电性

本文研究了压电、铁电晶体中负离子配位多面体的结晶方位与形变,提出了压电晶体中同一种负离子配位多面体的结晶方位是一致的.在铁电晶体中,负离子配位多面体发生形变,伴随着晶体发生顺电-铁电相变,并从这一基本过程出发,对铁电体相变的形成机理进行了讨论.     

Chemistry and Electrocrystallization of Organic Metals and Superconductors

Abstract

Considerable variation in the conditions of electrochemical crystal growth of TMTSF₂X (i.e., constant current versus constant potential, ambient versus inert atmosphere, etc.) and in the purity of the constituents (donor, electrolyte, solvent) does not significantly affect the unusual low-temperature properties of this class of materials. Our results suggest that the electrocrystallization procedure may be self-purifying by selecting for conducting crystal phases with constituents having specific oxidation potentials and solubility properties. However, doping solutions with structurally and chemically similar constituents (i.e., TMTTF, and IO^? ₄ in CIO^? ₄) leads to their incorporation in the crystal structure where they have a profound effect. Several mole percent of these dopants suppress superconductivity in the PF^? ₆ and CIO^? ₄ salts, and increase and broaden the metal-insulator phase transition.     

Hydrothermal Synthesis and Morphology of Thomsonite and Edingtonite

The hydrothermal treatment of different glasses of the composition 2 Na₂O–8 CaO–10 Al₂O₃– 20 SiO₂ and 2 BaO–2 Al₂O₃–6 SiO₂ at one kilobar pressure in a temperature-range between 80 °C and 230 °C lead to the formation of the zeolite-minerals thomsonite (orthorhombic symmetry space-group Pbmn, a = 13.05 Å, b = 13.09 Å and c = 13.22 Å), and edingtonite (orthorhombic symmetry, space-group: P2,2,2, a = 9.55 Å, b = 9.67 Å and c = 6.52 Å). Under the chosen hydrothermal conditions both mineral phases are formed in the whole temperature interval.     

Biocrystallization in Bacterial and Fungal Cells and Spores

A series of X-ray diffraction experiments were performed for the first time to study stress-induced biocrystallization (structural response to stress) in the bacteria E. coli, the spore-forming bacteria Bacillus cereus, and in cells and spores of the mycelial fungus Umbelopsis ramanniana. High-intensity areas with spacings of 90 and 44 Å are indicative of a periodically ordered arrangement (most likely nanocrystalline) of the bacterial nucleoid. For the starved bacteria Bacillus cereus, a peak at a spacing of 45 Å is also assigned to nanocrystalline complexes of DNA with the Dps protein. The spores of the fungus Umbelopsis ramanniana VKM F-582, as well as the spores of Bacillus cereus, form ordered arrays of DNA molecules with DNA-condensing acid-soluble proteins SASPs. Starved dehydrated mycelial cells of the fungus Umbelopsis ramanniana form ordered structures with spacings from 27 to 55 Å. A series of peaks reflect the formation of a number of ordered protein arrays, apparently with DNA, with continuously varying characteristic interplanar spacings.     

Preparation and characterization of PbSe nanopowder and quasi-ceramics

By means of the reduction of Pb(II) and Se(IV) with hydrazine, oval monodispersed PbSe nanoparticles characterized by sizes ～100 nm and the cubic symmetry were obtained. Their compaction and sintering into quasi-ceramic state were performed. The samples were investigated by means of scanning electron microscopy, X-ray diffraction and FTIR spectroscopy. The results obtained are discussed.     

Crystal and molecular structures of benz-p-nitroanilide and benz-p-methoxyanilide

The crystal structures of the two carboxylic amides C₁₃H₁₀N₂O₃ (I) and C₁₄H₁₃NO₂ (II) have been determined by direct methods and refined by full-matrix least squares. The predominant structural feature is the hydrogen bonding (N-H?O=C) which influences the conformations of both structures.     

Melting and short-range order in liquids and glasses

A theory is proposed to explain two-dimensional melting based on the gauge-invariant Lagrangian with spontaneous breaking (Higgs mechanism) or the SU(2) gauge field to U(1) symmetry. The first-order phase transition in two-dimensional melting may be strongly related to the asymptotic freedom-like interaction of the SU(2) gauge field in the case when the distance between each excited disk is shorter than a critical length, 2/ boxv;mboxv, near the melting temperature.     

Structural and spectral studies of N-trans-cinnamylidene-m-toluidine and N-trans-cinnamylidene-m-chloroaniline

N-trans-cinnamylidene-m-toluidine (1) C₁₆H₁₅N, and N-trans-cinnamylidene-m-chloroaniline (2) C₁₅H₁₂NCl form isomorphous crystals which are monoclinic, space group P2_l/c, with unit cell dimensionsa=5.967(2),b=13.793(3),c=15.048(5) Å, =91.97(3)° anda=5.868(2),b=13.788(4),c=15.191(4) Å, =91.87(3)°, respectively. The single-crystal X-ray structure determinations of the title compounds revealtrans structures. Ring (A) C_10–15 and ring (B) C_1–6, are practically planar in both structures with dihedral angels of 61.3(3) and 63.6(2)°, respectively.¹H nmr, u.v. and i.r. spectra are also reported.