Er∶LaAl3(BO3)4晶体的生长和光谱性质研究

采用助熔剂法生长了Er: LaAl3(BO3)4晶体.LaAl3(BO3)4晶体属正交晶系,晶胞参数a=0.93586(4) nm,b=0.79904(3) nm,c=0.43626 (6) nm,V=0.34595 nm3.测量了晶体在室温的吸收光谱和荧光光谱.该晶体吸收光谱能级丰富;在1533 nm波长处有较强的荧光光谱,对应于4I13/2→4I15/2的能级跃迁;晶体的荧光寿命为2.72ms.研究了晶体的热学性质,室温时的比热容大约为0.595 J/g·℃.     

Nd:YbVO4晶体的拉曼光谱和荧光光谱研究

用群论的方法计算了Nd:YbVO4晶体的拉曼活性振动模数目,在室温下测得了其极化拉曼谱线,并指认了在不同几何配置下,各振动模式所对应的频率.同时,测得了室温下晶体的吸收谱,得到了中心波长为808 nm吸收峰的半高宽为12 nm,并在J-O理论的基础上计算了晶体的光学参数,其三个晶场参数分别为Ω2=6.88945×10-20 cm2、Ω4=4.13394×10-20 cm2、Ω6= 4.54503×10-20 cm2,并由此得到4F3/2能级的荧光寿命为178.69 μs,1062 nm处的荧光分支比为48.85;,积分发射截面为2.7867 10-18 cm2.分别在808 nm、940 nm激发下测得晶体室温发射谱,观察到了Nd→Yb以及Nd←Yb间的能量传递现象.     

Yb:NdPO4晶体的生长与光谱性质

采用助熔剂自发成核法,以Li2CO3-2MoO3为助熔剂,生长出了Yb∶ NdPO4晶体.通过X射线粉末衍射和X射线能谱技术对所得的晶体进行了表征.结果表明,少量Yb3+掺入到了NdPO4晶体中,但并未改变NdPO4晶体的晶格结构.比较了Yb∶ NdPO4晶体和NdPO4晶体室温下的透过光谱.测量了室温下晶体的荧光光谱,泵浦光波长为332 nm.结果表明晶体的最强荧光发射峰位于995nm,归属于Yb3+从激发态2F5/2到基态2F7/2的电子跃迁.1059nm的发射峰归属于Nd3+从4 F3/2到4I11/2的电子跃迁.Nd3+的发射峰强度较弱,表明在室温下晶体中主要发生了Nd3+ →Yb3的能量传递.     

GdVO4晶体的生长及其性能研究

采用提拉法沿a轴和c轴生长出无色透明的GdVO4单晶,质量均超过50g.用X射线荧光分析法测得两个主要元素Gd和V的分凝系数都接近1.室温下测量了GdVO4晶体的X射线粉末衍射图,确定所获GdVO4晶体属于四方晶系,D194h-I41/amd空间群.通过晶体的锥光干涉图确定GdVO4晶体为单轴晶,光轴方向平行于c轴且光学均匀性比较好.利用高分辨X射线衍射仪测量GdVO4晶体的摇摆曲线,结果表明生长的GdVO4晶体的晶格完整性较好.通过浮力法测得其室温下密度为5.478g/cm3.透过波谱表明透过波长大于340nm.     

K2Al2B2O7晶体的热学性质研究

K2Al2B2O7(KABO)晶体是近年发现的一种有应用前景的深紫外非线性光学晶体,也是目前唯一一种可以生长出大尺寸单晶的BO3基团非线性光学晶体.KABO有可能用于固态激光器的266nm及193nm高功率输出.本文对该晶体的物理化学性质及热学性质进行了研究,KABO晶体不潮解,不溶于水、酒精等溶剂,可溶于盐酸,硝酸和磷酸等强酸;测得莫氏硬度为5.5～6.5,用浮力法测得其密度为2.47g/cm3;用差热分析(DTA)方法测量其熔点为1109.7℃.用热重分析(TGA)方法结合分解产物的粉末X射线衍射(XRD)分析,确定KABO在900℃以上开始分解,分解产物主要为KAl11O17和K2Al24O37;用热机械分析仪测量了其热膨胀系数,沿物理学轴X、Y、Z方向分别为8.4×10-6/K、7.7×10-6/K、1.65×10-5/K.在室温至300℃温度范围内测量了KABO晶体的比热变化,比热随温度的升高线性增大.在47.6℃和294.6℃时比热分别为1.0084J/g℃与1.39J/g℃.     

不同Li/Nb比Mg:In:Fe:LiNbO3晶体的光折变性能研究

采用提拉法生长了不同Li/Nb比(Li/Nb=0.85,0.94,1.05,1.20,1.38)的Mg:In:Fe:LiNbO3(LN)单晶.测试了Mg:In:Fe:LN晶体的红外透射光谱,紫外吸收光谱,抗光致散射能力,响应时间和指数增益系数.实验结果显示:Li/Nb=0.85晶体的OH-吸收峰在3481cm-1附近, Li/Nb=0.94、1.05、1.20的晶体的OH-吸收峰在3505cm-1附近,而Li/Nb=1.38晶体的OH-吸收峰有三个,分别在3466cm-1、3481cm-1和3518cm-1附近.随着Li/Nb比的增大,晶体的紫外吸收边发生紫移,抗光致散射能力增强,响应速度加快,指数增益系数增大.结果表明:Li/Nb=1.38的晶体是性能最为优良的光折变晶体材料.     

新型钨青铜型晶体Ca0.28Ba0.72Nb2O6的生长研究

研究了Ca0.28Ba0.72Nb2O6 (CBN-28)多晶料的制备和单晶的生长,用提拉法成功生长出CBN-28单晶.从X射线粉末衍射数据计算了CBN-28晶体的晶胞参数,并对其粉末衍射图各衍射峰进行了指标化.CBN晶体属四方晶系4mm点群.晶胞参数为a=1.2432(±2)nm,c=0.3957(±1)nm.采用浮力法测得其平均密度为5.372g/cm3,测得其莫式硬度为7,并通过测量CBN-28的介电性质,确定其居里点为260℃.     

CdLa2(WO4)4晶体的生长及发光性能的研究

以高温固相法成功合成了CdLa2(WO4)4多晶料,采用垂直坩埚下降法进行了晶体的生长.CdLa2(WO4)4晶体属于四方晶系白钨矿结构,其晶胞参数为:a=b=5.209 ?,c=11.325 ?,晶胞的体积为307.26 ?3,其密度为7. 494 g/cm3.在室温下测量了晶体的光致发光光谱、X射线激发发射光谱、光致发射衰减时间等.结果表明:在296 nm紫外光的激发下,样品在350~600 nm范围内具有宽阔的蓝绿发光带,发射峰的峰值为470 nm.并且其光致发射衰减时间为3.4 ns,在X射线激发下也有良好的发光性能.     

不同波长条件KDP晶体的非线性光学性质研究

采用Z扫描方法系统的研究了KDP晶体在不同激光波长条件下的非线性光学性质.当λ=355 nm,功率密度为57.92 GW/cm2和λ=532 nm,功率密度为105.94 GW/cm2时,KDP晶体均呈现强烈的反饱和吸收和自聚焦效应,其非线性吸收系数和非线性折射率分别为6.50×10 -2cm/GW,1.17×10 -2cm/GW和8.02×10 -7cm2/GW,6. 14×10 -7cm2/GW;而在1064 nm波长,功率密度为347.95 GW/cm2时KDP晶体并未表现出明显的非线性性质.结果表明,在短波长的激光作用下,KDP晶体更容易产生非线性效应,双光子吸收是KDP晶体非线性吸收的主要机制.     

富锂熔体中提拉法生长近化学计量比铌酸锂(LiNbO3)晶体

利用提拉法,在富锂(Li2O∶NbO3=58.5/41.5)熔体中生长了质量良好的近化学计量比铌酸锂单晶,其紫外吸收边位置为308nm,居里温度超过了1200℃.测量了其Z向晶片的压电系数d33,并且观察了Z向晶片的180°畴,结果证明除少数区域外,所生长晶体为单畴.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.