AuPH_3-C≡C-C_6H_5与(AuPH_3-C≡C)_2(1,4-C_6H_4)_2配合物激发态性质的密度泛函研究

用密度泛函方法优化了AuPH3-C≡C-C6H5(a)与(AuPH3-C≡C)2(1,4-C6H4)2(b)配合物的基态几何结构,并用含时密度泛函方法计算得出配合物a与b在CH2Cl2溶液中的发光光谱,计算结果与实验值符合得很好.计算得出两种Au(Ⅰ)配合物的最低能量吸收光谱分别为295.2 nm和353.1 nm,均属于C(2p)→Au(6p)的电荷转移(LMCT)修饰下的pπ(-C≡C-、■)→pπ*(-C≡C-、■)跃迁本质,并伴有Au(5d)→Au(6p)的金属中心电荷转移(MCCT)性质.配合物b近似由两个配合物a相连接而成,配合物b的分子轨道也由配合物a的分子轨道组合而成.由于轨道组合中存在pπ*或pπ相互作用,配合物b的最低能量吸收谱线的波长大于配合物a的相应值.Au(Ⅰ)的修饰作用使分子轨道的密度分布更具有规律性,使分子的轨道跃迁更活跃.     

二(吡啶-3-甲酸)铅Ⅱ金属配合物的密度泛函理论研究

标题化合物二(吡啶-3-甲酸)铅Ⅱ([PbⅡ(C5H4NCOO)2]在密度泛函B3LYP/LANL2DZ水平上进行了优化,计算结果显示此化合物具有V型的二配位几何构型.原子电荷分布分析显示,在形成此配合物的过程中,每一个吡啶-3-甲酸根负离子传递了-0.454 177 e电荷给铅离子.电子吸收光谱计算表明,在紫外区域存在两个吸收峰,它们对应于内配体π→π*电子跃迁及配体到金属的电荷转移跃迁(LMCT).标题化合物的部分热力学函数值也通过计算得到,并且得到了热力学函数与温度的相关关系.     

多吡啶配合物[Zn(4,4''-bpy)(CH3COO)(NO3)]n和[Y(bpy)2](NO3)3的合成、表征和晶体结构

通过自组装制得[Zn(4,4'-bpy)(CH3COO)(NO3)]n(配合物1)和[Y(bpy)2](NO3)3(配合物2).其中,4,4'-bpy为4,4'-联吡啶,bpy 为2,2'-联吡啶.对配合物进行了X-射线衍射结构表征.配合物1是聚合物,锌离子为6配位,4,4'-联吡啶作为双齿桥联配体使配合物呈线性一维链,而醋酸根作为双齿桥联配体和链间的π-π堆积作用,又使配合物形成一维网状的结构.配合物2中Y(Ⅲ)是10配位,2个2,2'-联吡啶各提供2个氮原子,3个硝酸根各提供2个氧原子参与配位.     

Eu~(3+)掺杂的La(Sal)_3 Phen的合成工艺及荧光性能

以1,10-邻菲罗啉和水杨酸为配体,稀土离子(Eu~(3+)和La~(3+))为中心配位原子,用水热法制备了组成为La_(0.95)Eu_(0.05)(Sal)_3Phen的微纳米尺寸金属有机配合物,考察了温度、pH值对合成配合物的影响,利用红外光谱仪、X射线衍射仪、扫描电镜等对其晶体结构和形貌进行了表征,并用激发和发射光谱分析了其荧光性能。结果表明:该配合物能够展示出Eu~(3+)的特征发射,能在激发光谱中读出水杨酸的π-π*电子跃迁、EuO电荷迁移带的宽带重叠和较长波长的Eu~(3+)f-f跃迁,也能在紫外吸收光谱中找到配体的特征吸收峰;温度90℃,pH=7条件下合成的样品结晶度、晶型规整性及荧光性能均优于其他工艺条件,合成中掺Eu~(3+)以及适当升温有利于结晶,pH值对样品合成的影响大于温度。     

三齿希夫碱水杨醛缩-1-α-胺苯基-2-萘酚及其铜(Ⅱ)配合物的结构与光谱性质研究

测定了希夫碱配体L(L:水杨醛缩-1-α-胺苯基-2-萘酚)及其铜(Ⅱ)配合物的晶体结构.在配合物中,Cu(Ⅱ)的配位环境为变形四方锥,配位原子为来自L的两个氧原子和一个氮原子以及来自吡啶配体的两个氮原子.用FT-IR、UV-vis、荧光光谱及热重对这些化合物进行了分析.光谱分析表明:配合物在490nm处有金属到配体的电荷迁移跃迁,在613nm处有d-d跃迁;荧光光谱表明配体的最大吸收和最大发射分别为303nm和390nm,形成配合物后,分别红移到338nm和420nm;从热重图上可以看到,配合物的分解分为两步,第一步失去配位的吡啶,第二步配合物分解.     

利用磁圆二色谱研究PVP—Co^3＋配合物的电荷转移跃迁

首次利用MCD研究了聚(4-乙烯基吡啶)—CO~(3+)配合物的电子跃迁及电荷转移跃迁。说明在含有d~6的PVP—Co~(3+)配合物中,不仅有d—d电子跃迁,同时还有金属→配体的t_(2g)→t_(1U)~(π*)电荷转移跃迁,这在吸收光谱中是不好解决的。     

[Zn（mn（t5）-NO2-phen）]配合物掺杂CdS的光-电转换特性

测量了标题配合物[Zn(mnt)(5-NO2-phen)] (mnt2-:1,2-二氰基乙烯-1,2-二硫醇离子. 5- NO2- phen :5-硝基-1,10-邻菲咯啉) 在二甲基亚砜(DMSO)和二甲基甲酰胺(DMF)等溶剂中的电子吸收光谱及DMSO中的电子发射光谱特性.研究发现标题配合物的紫外区吸收带270～280 nm、320～350 nm、360～390 nm本质上属于配体5-NO2-phen、mnt2-内部的πb→π*跃迁,可见光区450～490 nm本质上属于配体mnt2-到5-NO2-phen的荷移跃迁(LL′CT);在DMSO溶剂中,标题配合物在400～600 nm间呈现明显的荧光发射带.报道了掺杂有标题配合物[Zn(mnt)(5-NO2-phen)]的CdS-PVA复合膜的暗态导电性和光电导性,探讨发现标题配合物对半导体材料CdS具有光敏化作用.研究了[Zn(mnt)(5-NO2-phen)]对CdS的光敏化作用与其电子光谱间的关系.     

一种锌(Ⅱ)配合物的合成和晶体结构

合成了目标配合物:碘化双 -[3,4 -二甲氧基苯甲醛缩氨基硫脲]合锌(II) ,其结构通过单晶X-射线衍射法确定.晶体属单斜晶系,C2/c空间群.配合物分子中,锌(II)与两个硫原子、两个碘原子配位形成轻微畸变的四面体结构,每一个3,4 -二甲氧基苯甲醛缩氨基硫脲配体与锌离子处于同一平面内,在晶体中分子之间以氢键连接形成网状结构.     

[Co(L)(NO3)2]·CH3CN的合成和晶体结构

多吡啶配体2,3-二(2-吡啶基)-5,8-二甲氧基喹喔啉(L)与Co(NO3)2·6H2O反应生成配合物[Co(L)(NO3)2]·CH3CN,通过单晶衍射分析确证其结构.配合物的单晶结构中,Co(Ⅱ) 离子中心分别与配体L的2个吡啶环中的N原子和2个硝基的4个氧原子形成六配位的八面体配位结构,L以双齿配体形式参与配位.配合物通过π-π芳香体系堆积形成一维链状结构,芳香体系的面面叠加作用可能使配合物的结构更加稳定.     

CF3和CH3取代吡啶吡唑硼配合物的结构和吸收光谱的理论研究

采用密度泛函理论DFT/B3LYP在6-31G水平上研究了CH3和CF3取代吡啶吡唑硼配合物的几何和电子结构,在基态平衡构型的基础上通过含时密度泛函理论TD-DFT计算了其光谱性质.结果表明:氟代甲基吡啶甲基吡唑硼配合物(2b′)的配位键略强于甲基吡啶氟代甲基吡唑硼配合物(2b);二者的中心B原子对分子的结构不但起支撑稳定作用,还可以作为电子桥传输电子;当取代基交换位置时,苯环和吡唑环都可以作为空穴传输基团,电子传输基团仍为吡啶环,配合物的主要跃迁都属于配体内部的π→π*跃迁类型.     

Characterization of Ordovician carbonate reservoirs, southeastern Saskatchewan, Canada

The discovery of the prolific Ordovician Red River reservoirs in 1995 in southeastern Saskatchewan was the catalyst for extensive exploration activity which resulted in the discovery of more than 15 new Red River pools. The best yields of Red River production to date have been from dolomite reservoirs. Understanding the processes of dolomitization is, therefore, crucial for the prediction of the connectivity, spatial distribution and heterogeneity of dolomite reservoirs.The Red River reservoirs in the Midale area consist of 3～4 thin dolomitized zones, with a total thickness of about 20 m, which occur at the top of the Yeoman Formation. Two types of replacement dolomite were recognized in the Red River reservoir: dolomitized burrow infills and dolomitized host matrix. The spatial distribution of dolomite suggests that burrowing organisms played an important role in facilitating the fluid flow in the backfilled sediments. This resulted in penecontemporaneous dolomitization of burrow infills by normal seawater. The dolomite in the host matrix is interpreted as having occurred at shallow burial by evaporitic seawater during precipitation of Lake Almar anhydrite that immediately overlies the Yeoman Formation. However, the low δ18O values of dolomited burrow infills (-5.9‰～ -7.8‰, PDB) and matrix dolomites (-6.6‰～ -8.1‰, avg. -7.4‰ PDB) compared to the estimated values for the late Ordovician marine dolomite could be attributed to modification and alteration of dolomite at higher temperatures during deeper burial, which could also be responsible for its 87Sr/86Sr ratios (0.7084～0.7088) that are higher than suggested for the late Ordovician seawaters (0.7078～0.7080). The trace amounts of saddle dolomite cement in the Red River carbonates are probably related to "cannibalization" of earlier replacement dolomite during the chemical compaction.     

A computer generator for randomly layered structures

AcomputergeneratorforrandomlylayeredstructuresYUJia shun1,2,HEZhen hua2(1.TheInstituteofGeologicalandNuclearSciences,NewZealand;2.StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,ChengduUniversityofTechnology,China)Abstract:Analgorithmisintrod…     

海南岛地体及其毗邻陆缘晚中生代—新生代古地磁研究和构造演化

本文叙述了对海南岛及其毗邻大陆边缘白垩纪到第四纪地层岩石进行古地磁研究的全部工作过程。通过分析岩石中剩余磁矢量的磁偏角及磁倾角的变化,提出海南岛白垩纪以来经历的构造演化模式如下:早期伴随顺时针旋转而向南迁移,后期伴随逆时针转动并向北运移。联系该地区及邻区的地质、地球物理资料,对海南岛上述的构造地体运动提出以下认识:北部湾内早期有一拉张作用,主要是该作用使湾内地壳显著伸长减薄,形成北部湾盆地。从而导致了海南岛的早期构造运动,而海南岛后期的构造运动则主要是受南海海底扩张的影响。海南地体运动规律的阐明对于了解北部湾油气盆地的形成演化有重要的理论和实际意义。     

Exciton Seebeck in Molecular Systems

Various applications relevant to the exciton dynamics,such as the organic solar cell,the large-area organic light-emitting diodes and the thermoelectricity,are operating under temperature gradient.The potential abnormal behavior of the exicton dynamics driven by the temperature difference may affect the efficiency and performance of the corresponding devices.In the above situations,the exciton dynamics under temperature difference is mixed with     

Achieving Unusual States of Matter Under High Pressure

The elongation method,originally proposed by Imamura was further developed for many years in our group.As a method towards O(N)with high efficiency and high accuracy for any dimensional systems.This treatment designed for one-dimensional(ID)polymers is now available for three-dimensional(3D)systems,but geometry optimization is now possible only for 1D-systems.As an approach toward post-Hartree-Fock,it was also extended to     

《Chinese Science Bulletin》SUBJECT INDEX TO VOLUME 59(2014)

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An on-line scaling method for improving scalability of a database cluster

The explosive growth of the Internet and database applications has driven database to be more scalable and available, and able to support on-line scaling without interrupting service. To support more client's queries without downtime and degrading the response time, more nodes have to be scaled up while the database is running. This paper presents the overview of scalable and available database that satisfies the above characteristics. And we propose a novel on-line scaling method. Our method improves the existing on-line scaling method for fast response time and higher throughputs. Our proposed method reduces unnecessary network use, i.e. , we decrease the number of data copy by reusing the backup data. Also, our on-line scaling operation can be processed parallel by selecting adequate nodes as new node. Our performance study shows that our method results in significant reduction in data copy time.     

An improved R-tree based on childnode''s probability

R-Tree is a good structure for spatial searching. But in this indexing structure,either the sequence of nodes in the same level or sequence of traveling these nodes when queries are made is random. Since the possibility that the object appears in different MBR which have the same parents node is different, if we make the subnode who has the most possibility be traveled first, the time cost will be decreased in most of the cases. In some case, the possibility of a point belong to a rectangle will shows direct proportion with the size of the rectangle. But this conclusion is based on an assumption that the objects are symmetrically distributing in the area and this assumption is not always coming into existence. Now we found a more direct parameter to scale the possibility and made a little change on the structure of R-tree, to increase the possibility of founding the satisfying answer in the front sub trees. We names this structure probability based arranged R-tree (PBAR-tree).     

Integrating GIS Web services based on mediating architecture

The geographic information service is enabled by the advancements in general Web service technology and the focused efforts of the OGC in defining XML-based Web GIS service. Based on these models, this paper addresses the issue of services chaining,the process of combining or pipelining results from several interoperable GIS Web Services to create a customized solution. This paper presents a mediated chaining architecture in which a specific service takes responsibility for performing the process that describes a service chain. We designed the Spatial Information Process Language (SIPL) for dynamic modeling and describing the service chain, also a prototype of the Spatial Information Process Execution Engine (SIPEE) is implemented for executing processes written in SIPL. Discussion of measures to improve the functionality and performance of such system will be included.     

Tracking data management using topology of moving object database system for moving object constrained trajectory in LBS application

Advances in wireless technologies and positioning technologies and spread of wireless devices, an interest in LBS (Location Based Service) is arising. To provide location based service, tracking data should have been stored in moving object database management system (called MODBMS) with proper policies and managed efficiently. So the methods which acquire the location information at regular time intervals then, store and manage have been studied. In this paper, we suggest tracking data management techniques using topology that is corresponding to the moving path of moving object. In our techniques, we update the MODBMS when moving object arrived at a street intersection or a curved road which is represented as the node in topology and predict the location at past and future with attribute of topology and linear function. In this technique, location data that are corresponding to the node in topology are stored, thus reduce the number of update and amount of data. Also in case predicting the location,because topology are used as well as existing location information, accuracy for prediction is increased than applying linear function or spline function.