KH_2PO_4和（CH_3NHCH_2COOH）_3CaCl_2在高压下的状

在活塞圆筒式Ｐ～Ｖ关系测量装置上，研究了ＫＨ＿２ＰＯ＿４（ＫＤＰ）和（ＣＨ＿３ＮＨＣＨ＿２ＣＯ－ＯＨ）＿３ＣａＣＩ＿２［Ｔｒｉｓ－ｓａｒｃｏｓｉｎｅｃａｌｃｉｕｍｃｈｌｏｒｉｄｅ（ＴＳＣＣ）］在室温下、４．５ＧＰａ内的ｐ～Ｖ关系。实验结果表明：ＫＤＰ在２．１ＧＰａ左右有一个相变；ＴＳＣＣ在０．８ＧＰａ和３．２ＧＰａ左右各有一个相变。本工作还给出了它们在相变前后的状态方程，以及它们的格临爱森参数γＯ、体积模量Ｂ＿ｏ和Ｂ＿ｏ的压力导数Ｂ＿ｏ。     

一类新颖含C60复合材料的合成及其光限制效应的研究

报道了在Ｃ６０与ＮＨ２（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３中的胺基反应生成Ｃ６０－ＮＨ２（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３物质后引入ｒ－缩水甘油醚基丙基三甲氧基硅烷「ＣＨ２ＯＣＨＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３，３－Ｇｌｙｃｉｄｏｘｙｐｒｏｐｌｔｒｉｍｅｔｈｏｘｙｓｉｌａｎｅ，简称ＫＨ５６０」与二甲基二乙氧基硅烷「（ＣＨ３）２Ｓｉ（ＯＣ２Ｈ５）２，Ｄｉｅｔｈｏｘｙｄｉｍｅｔｈｙｌｓｉｌａｎｅ     

在He和Ne的流动余辉中POCl3的解离动力学

本文利用流动余辉技术研究了亚稳态原子Ｈｅ（２＾３ｓ）和Ｎｅ（＾３ｐ０．２）与ＰＯＣｌ３分子的传能反应，获得了激发态碎片ＰＯ（Ａ）和ＰＯ（Ｂ）的发射光谱，测定了Ｈｅ（２＾３ｓ）与ＰＯＣｌ３反应中ＰＯ（Ａ）和ＰＯ（Ｂ）的形成速率常数，其数值分别为：ＫＰＯ（Ａ）＝３．６８×１０＾－１１ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１Ｓ＾－１和ＫＰＯ（Ｂ）＝９．４０×１０＾－１１ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１·Ｓ＾－１     

富电子膦硫混配钴簇合物Co6S8[P（OCH3）3]6的电化学研究

利用循环伏安法研究了膦硫混配原子簇化合物Ｃｏ６Ｓ８「Ｐ（ＯＣＨ３）３」６的电化学行为,结果表明Ｃｏ６Ｓ８「Ｐ（ＯＣＨ３）３」６在ＣＨ２Ｃｌ２训可观察到三个可逆氧化还原过程,其电子转移过程为;Ｃｏ６Ｓ８「ｐ（ｏｃｈ３）３」６－＝＾（－Ｅ,＋Ｅ）Ｃｏ６Ｓ８「Ｐ（ＣＯＨ３０３」６ｙ０＝（＾－ｅ,＋ｅ）Ｃｏ６Ｓ８「Ｐ（ＯＣＨ３）３」６＾＋＝＾（－ｅ,＋ｅ）Ｃｏ６Ｓ８「Ｐ（ＯＣＨ３）３」６＾２＋并探讨了其电     

meso-四(4-磺基苯基)卟啉(TPPS)在微乳液中的行为研究

本文首次研究了ｍｅｓｏ－四（４－磺基苯基）卟啉（ＴＰＰＳ）在Ｏ／Ｗ型微乳液（Ｔｒｉｔｏｎ Ｘ－１００－壬烷－正戊醇－水）体系中的电子吸收光谱变化，计算了ＴＰＰＳ的电离常数Ｋａ及二聚常数ＫＤ。     

磺化酞菁镓、钒、铝、锌在水、醇、胶束中的聚合行为的研究

采用分光光度法研究了四磺化酞菁镓,钒,铝和二磺化酞菁锌在水,醇－水,胶束体系中的聚合行为,测定了配合物的二聚常数。结果表明,ＡｌＴＳＰｃ形成二聚体是一个慢反应,而ＧａＴＳＰｃ,ＺｎＢＳＰｃ和ＶＯＴＳＰｃ的二聚体形成是快速过程。     

NEOCLASSICAL TRANSPORT IN A TOKAMAK WITH ELECTRIC SHEAR

ＮＥＯＣＬＡＳＳＩＣＡＬＴＲＡＮＳＰＯＲＴＩＮＡＴＯＫＡＭＡＫＷＩＴＨＥＬＥＣＴＲＩＣＳＨＥＡＲＷＡＮＧＺｈｏｎｇ ｔｉａｎ1,ＧＬｅＣｌａｉｒ2(1.ＳｏｕｔｈｗｅｓｔｅｒｎＩｎｓｔｉｔｕｔｅｏｆＰｈｙｓｉｃｓ,Ｃｈｅｎｇｄｕ610041;2.ＣｅｎｔｅｒＣａｎａｄｉｅｎｄｅＦｕｓｉｏｎＭａｇｎｅｔｉｑｕｅ,Ｃａｎａｄａ)　　Ａｂｓｔｒａｃｔ:Ｎｅｏｃｌａｓｓｉｃａｌｔｒａｎｓｐｏｒｔｔｈｅｏｒｙｆｏｒａｔｏｋａｍａｋｉｎｔｈｅｐｒｅｓｅｎｃｅｏｆａｌａｒｇｅｒａｄｉａｌｅｌｅｃｔｒｉｃｆｉｅｌｄｗｉｔｈｓｈｅａ…     

沙蚕磷草酸盐的合成与光谱表征

用１－二甲氨基－２,３－二氯丙烷和Ｏ,Ｏ－二甲基－二硫代磷酸盐反应合成了一种新的有机磷杀虫剂沙蚕磷,还制备了它的草酸盐。用１Ｈ、１３Ｃ核磁共振波谱、红外光谱及质谱法表征了沙蚕磷草酸盐的分子结构,结果表明反应产物是１,３－二取代产物。沙蚕磷的分子结构为（ＣＨ３）２Ｎ＋ＨＣＨ［ＣＨ２ＳＰ（Ｓ）（ＯＣＨ３）２］２Ｃ２Ｏ４Ｈ－［Ｏ,Ｏ,Ｏ′,Ｏ′－四甲基－Ｓ,Ｓ′－（２－Ｎ,Ｎ－二甲氨基丙撑）－双－二硫代磷酸酯草酸盐］。     

ELECTRON MOMENTUM SPECTRA OF EXCITED He(2~1S) AND He(2~3S)

ＥＬＥＣＴＲＯＮＭＯＭＥＮＴＵＭＳＰＥＣＴＲＡＯＦＥＸＣＩＴＥＤＨｅ（２１Ｓ）ＡＮＤＨｅ（２３Ｓ）ＣｈｅｎＺｈａｎｇｊｉｎＳｈｉＱｉｃｕｎＣｈｅｎＪｉＸｕＫｅｚｕｎＤｅｐａｒｔｍｅｎｔｏｆＭｏｄｅｒｎＰｈｙｓｉｃｓ，ＵｎｉｖｅｒｓｉｔｙｏｆＳｃｉｅｎ...     

PUSHING THE ENVELOPE IN RAMAN SPECTROSCOPY

ＰＵＳＨＩＮＧＴＨＥＥＮＶＥＬＯＰＥＩＮＲＡＭＡＮＳＰＥＣＴＲＯＳＣＯＰＹＧ．Ｄ．Ｐｉｔｔ（ＵｎｉｖｅｒｓｉｔｙｏｆＬｅｅｄｓａｎｄＲｅｎｉｓｈａｗｐｌｃＵ．Ｋ）ＮｅｗｔｅｃｈｎｉｑｕｅｓｈａｖｅｂｅｅｎｄｅｖｅｌｏｐｅｄｆｏｒＵＶＲａｍａｎｍｉｃｒ...     

Branching ratio and L2 + L3 intensities of 3d-transition metals in phthalocyanines and the amine complexes

L(2,3) inner-shell excitation spectra were obtained by electron energy-loss spectroscopy (EELS) for the divalent first transition series metals in phthalocyanine complexes (MPc) such as titanium oxide phthalocyanine (TiOPc), fluoro-chromium phthalocyanine (CrFPc), manganese phthalocyanine (MnPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), nickel phthalocyanine (NiPc) and copper phthalocyanine (CuPc). It was found that the value of normalized total intensity of I(L2 + L3) was nearly proportional to the formal electron vacancies of each 3d-state, and the values of the branching ratio, I(L3)/I((L2 + L3), represented a high-spin-state rather than low-spin-state for MnPc, FePc and NiPc. EELS was also applied to charge-transfer complexes of FePc with an amine such as pyridine or gamma-picoline. It was concluded that their I(L2 + L3) intensity of Fe showed the decrease in vacancies of 3d-states on the formation of the charge-transfer complex with these amines, which suggests some electron transfer from the amine to Fe in phthalocyanine. The EELS study provides beneficial information for investigating the electronic states of the specific metal sites in organic materials.     

两亲性金属酞菁的催化性能研究

采用耗氧法研究了4种金属酞菁配合物[α-四(对羧基苯氧基)金属酞菁(Zn,Co)、β-四(对羧基苯氧基)金属酞菁(Zn,Co)]对0.1mol.L-1亚硫酸钠的催化氧化性能,考察了配合物中心金属和取代基的位置对催化活性的影响。研究结果表明中心离子相同时,β位四取代(对羧基苯氧基)金属酞菁的催化活性优于α位;取代基位置相同时,酞菁钴的催化氧化性优于酞菁锌。且β-四(对羧基苯氧基)酞菁钴的浓度为1.00×10-4mol.L-1时,对亚硫酸钠的催化氧化性能最高。     

酞菁化合物合成及光谱性能研究

为有效对抗高、超光谱成像侦察威胁,实现迷彩绿色涂料与植物的"同谱同色",本文基于酞菁与叶绿素卟啉结构的相似性,开展酞菁化合物合成及植物光谱特征拟合研究。构建吸电子取代基团和二价过渡族中心离子的平面酞菁结构,采用DBU催化法和自制合成装置合成酞菁化合物,探究最佳合成条件和提纯方法,采用分光光度计测试产物的吸收光谱和反射光谱,研究中心离子与聚集方式对酞菁化合物光谱性能的影响。实验结果表明,在催化剂作用下,四硝基金属酞菁在240~250℃时反应时间最短;钴酞菁比铁、锌、铜等作为中心取代离子形成的酞菁产物具有更尖锐的吸收峰,与绿色植物光谱曲线更相似;酞菁化合物的光谱反射曲线随温度、纯度及分散状态对产物聚集状态影响而产生移动。在220~240℃下合成20~30 min的四-硝基钴酞菁吸收光谱符合酞菁化合物Q带吸收特征,且其峰值波长与植物光谱相拟合,为酞菁类颜料在军事、纺织、染料、仿生等领域的应用提供了新方法和新途径。     

四氨基钴酞菁紫外-可见光谱量子化学研究

四氨基钴酞菁是一种很有前途的可见光催化剂,为丰富和完整该物质结构性质及反应活性的理论体系,尤其是其光谱性质的量子化学研究,利用量子化学计算模拟和实验研究相结合的方式对四氨基钴酞菁的紫外-可见光谱进行了比对研究。通过实验证明,四氨基钴酞菁的二甲基甲酰胺(DMF)溶液在324.98和709.94 nm处出现两个明显的吸收峰。在密度泛函法的B3LYP/3-21G*水平上,采用含时密度泛函(time-dependent density functional theory,TD-DFT)方法模拟四氨基钴酞菁的紫外-可见吸收光谱显示,得到了两个吸收谱带分别在321.41和709.92 nm处,与实验值基本吻合,证明密度泛函理论在四氨基钴酞菁的量子化学理论研究是有效可靠的。通过量子计算还确定了每个吸收峰中各个电子跃迁的贡献率：在326.22 nm处的吸收主要是电子从轨道152到163 LUMO的跃迁;在314.42 nm处的吸收主要是电子从轨道149到164 LUMO+1的跃迁;在747.57 nm处的吸收主要是电子从轨道162 HOMO到163 LUMO的跃迁;在676.01 nm处的吸收主要是电子从轨道162 HOMO到164 LUMO+1的跃迁。这些模拟数据对实验研究提供了极大的理论补充,四氨基钴酞菁的紫外-可见光谱量子化学研究对后续实验指导及应用有十分重要的理论意义。     

Strong nonlinear optical refractive effect of self-assembled multilayer films containing tetrasulfonated iron phthalocyanine

Multilayer films containing anionic iron phthalocyanine tetrasulfonate (FePcTsNa₄) and cationic poly(diallydimethyl ammonium chloride) were prepared using electrostatic self-assembled layer-by-layer technique. The growth of the film was monitored by ultraviolet-visible absorption spectroscopy, and the morphology of the film was characterized by atomic force microscopy. Polarized visible spectra showed that macrocycles of FePcTsNa₄ in the film presented a flat orientation relative to the plane of the solid substrates. The third-order nonlinear optical properties of the film were studied by using Z-scan technique with laser duration of 21 ps at the wavelength of 532 nm. The FePcTsNa₄/PDDA film exhibited strong self-focusing effect with n₂ value of 4.13 × 10⁻¹⁵ m²/W, which is 4 orders larger than that of FePcTsNa₄ aqueous solution.     

新型不对称酞菁的电致发光性质研究

制作了以3种新璎不对称酞菁铜为发光层的电致发光器件并研究了其电致发光性质.3种新型不对称酞菁铜为2(3)-(对叔丁基苯氧基)酞菁铜(1),2(3),9(10),16(17)-三-(对叔丁基苯氧基)酞菁铜(2)和2(3),16(17)-二-(对叔丁基苯氧基)酞菁铜(3).其中以(1)和(3)为发光层的器件结构ITO/NPB(40 nm)/Phthalocynine(Pc)(30 nm)/AlQ(43.8 nm)/LiF(0.5 nm)/Al(120 nm).其中以(2)为发光层的器件结构为:ITO/NPB(30 nm)/Pc(30 nm)/BCP(20 nm)/AlQ(30 nm)/LiF(0.5 nm)/Al(120 nm).以(1),(2)和(3)为发光层与Q带栩关联的发射波长分别出现在869和1 062 nm;1 050和1110 nm;和1 095和1 204 nm.上述发射波长的不同是因为取代基的数目和真空镀膜的分子聚集态不同造成的,所以3种不对称酞菁铜的发射峰值和半峰宽差别较大,而且由此也引起斯托克司位移的不同.     

四氨基钴酞菁的分子结构和红外光谱量子化学研究

四氨基钴酞菁作为一种很有前途的光敏剂,其光谱研究具有十分重要的意义。以密度泛函的B3LYP/3-21G*方法对四氨基钴酞菁的四种构型进行结构优化,计算出最稳定结构的能量,并模拟计算四氨基钴酞菁的红外光谱,模拟得出的红外光谱与实验所得的振动带有很好的拟合性。     

6-NO_2-BTAMB与钴显色反应的研究与应用

研究了6-NO2-BTAMB与钴显色反应。实验表明,在pH6.2—7.4(CH2)6N4-HCl体系中,钴与试剂定量地形成稳定的蓝绿色络合物,表观摩尔吸光系数ε650=1.18×105L·mol-1.cm-1;钴浓度在0—6μg/10mL范围内符合比耳定律。用于VB12和钴分子筛中微量钴的测定,结果令人满意。     

Charge transfer at F<Subscript>16</Subscript>CoPc and CoPc interfaces to Au

We analyze the electronic properties of the interfaces between cobalt phthalocyanine (CoPc), as well as fluorinated cobalt phthalocyanine (F₁₆CoPc), and an Au(100) single-crystal using X-ray photoemission spectroscopy and valence band ultraviolet photoemission spectroscopy. Our data demonstrate that for the monolayers of both materials a charge transfer occurs from the substrate to the center of the organic molecules resulting in a central Co(I) ion. This leads to the conclusion that this effect essentially is fluorination- and ligand-independent.     

Improvement of the efficiency of phthalocyanine organic Schottky solar cells with ITO electrode treatment

The devices investigated in this work consisted of an indium tin oxide (ITO)-coated glass substrate, phthalocyanine (Pc) layer and an aluminum electrode. The Schottky cell exhibits optimal performance with one ohmic and one barrier contact. The work function of the ITO film is typically around 4.5–4.8 eV, while the HOMO level of phthalocyanine films is typically around 5.2 eV. It is known that surface treatment of ITO can change its work function. We investigated various ITO surface treatments for improving the performance of phthalocyanine-based Schottky solar cells. We found that cells of ITO treated with HCl and UV ozone exhibited the best performance. Four different phthalocyanines (Pcs), namely nickel phthalocyanine (NiPc), copper phthalocyanine (CuPc), iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc) were investigated. A power conversion efficiency as high as 10% was achieved for the CuPc cell with monochromatic excitation at 632.8 nm, with a light intensity of 2.7 W/cm². PACS 72.40.+w; 73.61.Ph