三水硝酸铈与18-冠-6配合物的相平衡研究

采用半微量相平衡方法研究了三元体系Ｃｅ（ＮＯ３）３·３Ｈ２Ｏ－ １８Ｃ６－ Ｃ２Ｈ５ＯＨ 在３０３．１５Ｋ 时的溶解度,测定了各饱和溶液的折光率。该体系在３０３．１５Ｋ 时仅生成一种化学计量的配合物Ｃｅ（ＮＯ３）３·１８Ｃ６·３Ｈ２Ｏ。同时试验考察了相平衡过程中水的行为,合成分离了固态配合物,用化学分析,ＩＲ、ＤＴＧ、ＴＧ 及电导测定研究了配合物的组成和性质。     

八氰钨-钴异金属配合物的合成、结构和理论研究

以八氰钨为构筑单元,与过渡金属Co~Ⅱ离子合成了一个具有三维结构的八氰钨-钴配位聚合物Co_2~Ⅱ(4-Mepy)8[W~Ⅳ(CN)_8](4-Mepy=4-甲基吡啶)。通过X-射线单晶衍射、元素分析和红外光谱对标题配合物进行了结构表征。单晶结构解析表明,标题配合物属于正交晶系,Fddd空间群,部分晶体学参数为:a=13. 939(4)■,b=26. 397(7)■,c=30. 168(8)■,V=11 100(5)■3,z=8,Dc=1. 502 g/cm~3,μ=2. 711 mm~(-1),F(000)=5 056,R=0. 046 8[I2σ(I)],wR=0. 106 2[I2σ(I)]。Co~Ⅱ离子中心均处于压缩Co N6八面体中,CoⅡ和WⅣ离子通过4个CN基团与相邻异金属W彼此交替相连,形成三维网状结构。此外,基于密度泛函理论(DFT)对八氰钨-钴配位聚合物进行了量子化学计算,计算结果与实验吻合。     

三水硝酸与18—冠—6配合物的相平衡研究

采用半微量相平衡方法研究了三元体系Ｃｅ（ＮＯ３）３．３Ｈ２Ｏ－１８Ｃ６－Ｃ２Ｈ５ＯＨ在３０３．１５Ｋ时的溶解度,测定了各饱和溶液的折光率。该体系在３０３．１５Ｋ时仅生成一种化学计量的配合物Ｃｅ（ＮＯ３）３．１８Ｃ６．３Ｈ２Ｏ。     

2,6-二甲基吡啶与1-己烯反应烯烃插入过程的理论研究

本论文使用密度泛函理论详细研究了2,6-二甲基吡啶与1-己烯反应的烯烃插入过程.计算结果表明,与2,1-插入路径相比,1,2-插入路径具有较低的插入能垒和较好的热力学性质.1,2-插入模式下,si面插入比re面插入在动力学和热力学上更为有利.电子因素在区域选择性的实现中起着至关重要的作用.最可行路径中关键过渡态的稳定性...     

二苯并18-冠-6-双苦胺萃取光度法测定微量钾的研究

本文报导二苯并18-冠-6、双苦胺与钾离子形成三元络合物萃取到有机相进行分光光度法测定钾,表观摩尔吸光系数为4×10~4。     

Fe配合物催化的乙醛氢化反应机制的理论研究

利用Gaussian 03程序对Fe配合物催化的乙醛氢化反应机制进行了理论研究。此氢化反应包括两个过程:氢转移过程和氢活化过程。对于氢活化过程,本文根据是否需要乙醇的协助提出了两种反应路径:路径1是Fe的配合物单独与H2进行加成反应,路径2是Fe配合物在乙醇的协助下与H2进行加成反应。利用密度泛函理论对反应历程中所涉及到所有反应物、过渡态和产物的基态进行优化,并利用Gaussian 03程序中的NBO关键字对优化得到的反应物、过渡态和产物的构型进行了NPA电荷分析。通过比较反应能垒得到路径2是比较容易发生的反应,并得出在Fe配合物催化氢化乙醛的反应循环中,氢转移过程为决速步的结论。     

配合物[C10H9N]2CuBr2的制备、结构分析及其对乙醇氧化羰化反应的催化活性

以CuBr₂和4-甲基喹啉为原料, 在乙醇溶剂中制备了含溴铜(Ⅱ)配合物。通过FTIR、EA、XRD和ICP-AES表征, 初步确定了配合物分子结构为[C₁₀H₉N]₂CuBr₂;采用密度泛函理论计算对其结构、自然原子电荷和前线轨道进行分析, 进一步确定分子结构的可靠性, 并将该配合物应用于乙醇氧化羰化合成碳酸二乙酯催化反应中。结果表明, 在催化剂浓度为0.075 g·ml^-1, 反应温度为100℃, 反应压力为3.5 MPa, 反应时间为4 h的条件下, 乙醇的转化率达到21.5%。通过探讨反应机理, 认为该配合物催化剂稳定性适中, 有利于主反应控制步骤CO的插入反应, 有助于中间体的形成, 从而使催化活性得到提高。     

环金属铱配合物的量子理论研究

本文采用密度泛函方法研究了四个环金属铱配合物Ir(pty-R)2(acac)[pty=3-(4-R-苯基)-4,5-二甲基-1,3-噻唑-2-亚基,acac=乙酰丙酮,R=H(1),Br(2),phenyl(3),CN(4)]的几何结构、电子结构和光谱特性。计算得到的基态键长与相应的实验值符合得较好。1～4的最低能吸收和发射分别在384、376、388、392 nm和475、484、487、500 nm。其最高占据分子轨道主要占据在金属和双齿配体上,而最低空轨道是!*(pty)型轨道。因此,1～4的最低能吸收和发射被指认为[d(Ir)+π(pty)/π(acac)→π*(pty)]的激发,具有金属到配体和发生在配体上的MLCT/I(L) LCT混合跃迁特征。     

含二苯并-18-冠-6单元的酰胺型双臂冠醚化合物的合成

合成了２个含二苯并－１８－冠－６单元的酰胺型双臂冠醚化合物,其结构经ＩＲ、＾１ＨＮＭＲ、ＭＳ和元素分析确证,该２个化合物都不具有液晶性,探讨了冠醚结构与液晶性的关系。     

新型冠醚及其超分子配合物研究的新进展

介绍了冠醚化学的产生、发展及应用,详细介绍了：几种新型臂式冠醚及其超分子金属配合物的合成;取代冠醚及其金属配合物的合成及应用;新型氮杂冠醚及其金属配合物的合成及应用。并对冠醚化学的发展进行了展望。     

水化在18-冠醚-6对K+和Na+选择过程中作用的理论研究

A combination of molecular dynamics (MD) and density functional theory (DFT) calculations were used to study the hydration structures of K+ and Na+ ions under the confinement of 18-crown-6 in order to identify the role of water in the selectivity of 18-crown-6 towards K+. The radial distribution functions, coordination numbers, orientation structures and interaction energies were analyzed to investigate the hydration of K+ and Na+ in 18-crown-6/cation complexes. All calculations of K+ and Na+ in bulk water were also conducted for comparison. The simulation results show that the orientation distributions of the water molecules in the first coordination shell of K+ are more sensitive to the confinement of 18-crown-6 than those of Na+. It is more favorable to confine a K+ in 18-crown-6 than a Na+ in terms of interaction energy. Good agreement is obtained between MD results and DFT results.     

含能材料分子N8H8结构与性质的理论研究

采用密度泛函理论的b3lyp方法在6-311＋＋G＊＊基组上对30种N8H8链状异构体进行了理论计算,并应用分子中的原子理论（Atoms In Molecules,AIM）和自然键轨道理论（Nature Bond Orbital,NBO）分析了这些化合物相对稳定性和成键特征,G3MP2方法计算了各异构体的能量及生成热。结果表明：N8H8链状异构体中,含有N=N双键特征的异构体稳定性较好,影响氮氮键键长变化的主要因素是N原子孤对电子到相邻的氮氮键的超共轭作用;所有异构体中α3的生成热最大,β15的密度最大。     

苦味酸含能离子盐的结构、生成热及爆炸性能理论研究

运用密度泛函理论DFT-B3LYP方法对5种苦味酸系列含能离子盐:苦味酸铵、苦味酸氨基脲、苦味酸碳酰肼、苦味酸氨基胍和苦味酸1,5-二氨基四唑进行了几何结构优化及红外振动分析,计算出生成热,并在此基础上,运用Kamlet-Jacobs方程估算出该类离子盐的爆速和爆压.     

铁酸系列复合金属氧化物铝热反应焓的理论研究

运用密度泛函理论(DFT),在Material Studio程序包的GGA-PBE、GGA-BLYP、GGA-PW91泛函结合DNP基组水平上,计算了7种常见金属氧化物的铝热反应焓。将计算值与实验值进行对比,确定出最佳计算基组水平。在此基础上,对6种铁酸系列复合金属氧化物(CuFe2O4、NiFe2O4、CoFe2O4、MgFe2O4、ZnFe2O4、MnFe2O4)的铝热反应焓进行了理论计算,并运用盖斯定律导出其标准摩尔生成焓。结果表明,GGA-PBE/DNP方法计算的标准摩尔反应焓精度高、误差小,平均误差7.072kJ/mol;在GGA-PBE/DNP水平下,6种复合金属氧化物的铝热反应焓分别为-3 695.02、-3 388.53、-3 380.13、-841.06、-3 142.57和-2 738.40kJ/mol,与等量物理混合金属氧化物的铝热反应焓相差不大。6种复合金属氧化物标准摩尔生成焓为-992.96、-1 092.12、-1 090.13、-1 431.13、-1 185.15和-1 311.78kJ/mol。     

[Fe(O)OH]~⊕活化甲烷反应的理论研究

采用密度泛函理论研究了气相中[Fe(O)OH]⊕与甲烷的反应机理。用B3LYP方法优化了势能面上各反应路径的过渡态和中间体等各驻点的结构,并通过振动分析和内禀反应坐标法对过渡态和中间体进行了确认,计算提出了两条可能的反应路线,揭示了[Fe(O)OH]⊕与甲烷的反应机理,同时对反应中存在的势能面交叉现象进行了研究,确定了最低势能交叉点处的作用机制。     

Zn3V2O8的电子结构与光学性质的理论研究

采用平面波超软赝势密度泛函理论的方法研究了Zn3V2O8的能带结构、电子态密度和光学特性.能带结果显示Zn3V2O8呈间接带隙的绝缘体型能带,其禁带宽度为2.9 eV.详细的电子态密度结果显示其费米面上的态密度达到20 e/eV,费米能级附近的能级由Zn3p、V3p和O2p电子形成,Zn3d和O2s之间有强的杂化作用.介电性能结果显示在4.4 ～5.7 eV附近有强的吸收峰,在20.6 eV附近有一个次强吸收峰;吸收光谱显示在6.8 eV处有强吸收,在20.7 eV处有一个较弱的吸收峰.     

六氮苯芳香性的量子化学计算研究

采用密度泛函方法,在B3LYP/6-311 G(d,p)水平,对六氮苯环分子进行了几何结构全优化。发现六氮苯环分子具有类似苯的键长平均化,分子结构平面化。在同键反应的基础上,用基团加和法,在B3LYP/6-311 G(d,p)水平,估算了六氮苯环的磁化率增量和各向异性磁化率,六氮苯环的磁化率增量和各向异性磁化率值都为负值。在同一水平估算了六氮苯环分子的核独立化学位移,与在同一水平上估算的苯等物质的核独立化学位移进行比较。结果都表明六氮苯环分子具有较强的芳香性。     

Theoretical Studies on the Structures,Densities, Detonation Properties and Thermal Stability of Tris(triazolo)benzene and its Derivatives

To look for superior and safe high-energy density materials (HEDMs), tris(triazolo)benzene and its R = ?CN, ?NHNO₂, ?N(NO₂)₂, ?NH₂, ?N(NH₂NO₂), and ?N(NO₂ONO₂) derivatives were studied at the B3LYP/6-311G(d, p) level of density functional theory (DFT). The energy content of the molecules was evaluated by calculating standard heats of formation, using isodesmic reaction. The results showed that all tris(triazolo)benzene derivations had high and positive heat of formation. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the tris(triazolo)benzene derivatives. Most tris(triazolo)benzene derivatives for Ring-R had large bond dissociation energies (BDEs) which were over 140kJ · mol^{? 1}except R = ?N(NO₂ONO₂), which showed that the tris(triazolo)benzene derivatives had good thermodynamic stability. Impact sensitivity was evaluated using frontier orbital energies and characteristic heights (H₅₀). These results indicated that incorporation with ?NH₂ is an effective means to decrease molecular sensitivity. Detonation velocities and pressures were estimated using modified Kamlet-Jacobs equations, based on the theoretical densities and heats of formation. These derivatives possess excellent detonation properties, for C, E, and, the detonation velocity are 9.38, and 9.98 km.s^?1, and the detonation pressure are 43.68, and 48.41Gpa, respectively, the detonation performances are better than cyclotetramethylenetetranitramine (HMX). The detonation character of A, B, D, G, and F also are very close to that of HMX. Taking detonation performance and stability into consideration, the most of tris(triazolo)benzene derivatives may be good candidates of high energies materials.     

Theoretical Study for High-Energy-Density Compounds Derived from Cyclophosphazene. IV. DFT Studies on 1,1-Diamino-3,3,5,5,7,7-hexaazidocyclotetraphosphazene and Its Isomers

In the present study, a theoretical study of 1,1-diaminohexaazidocyclotetraphophazene (DAHA) and its isomers has been performed, using quantum computational density functional theory (B3LYP and B3PW91 methods) with 6-31G* and 6-31G** basis sets implemented in Gaussian 03 program suite. Molecular structure and bonding, vibrational frequencies, Milliken population analysis, and natural bond orbit (NBO) have been studied. The heats of formation from atomization energies have also been calculated based on the optimized geometry. The obtained heats of formation data are compared with their homologous cyclophosphazene in order to demonstrate the accuracy of the methods, which indicate that the studied compounds might be potentially used as high energetic materials. In addition, the relative stability of five isomers have been deduced based on the total energy and the gap of frontier orbital energies.     

Impact of Functionalized Polystyrenes as the Electron Injection Layer on Gold and Aluminum Surfaces: A Combined Theoretical and Experimental Study

At metal/organic interfaces, the insertion of an organic monolayer can significantly modify the surface properties of the substrate, especially in terms of charge injection across the interface. Herein, we study the formation of an insulating monolayer of morpholine or amine-functionalized polystyrene on Al(111) and Au(111) surfaces and its impact on surface work-function and charge injection. First-principles calculations based on Density Functional Theory have been carried out and point to a significant decrease in the work-function of modified metal surfaces; this is in very good agreement with ultraviolet photoemission spectroscopy measurements performed on the Au(111) surface. In addition, a bilayer cathode, consisting of a thin film of high-work-function metal, such as Al and Au, and a layer of amine-functionalized polystyrene, was also fabricated and tested in organic light-emitting diodes. Such bilayer structures exhibit substantially enhanced efficiency when compared with controls without the functionalized polymers. Our combined theoretical and experimental investigation gives insight into how a thin layer of a commodity polymer can be used to transform rather high-work-function metals into high-performance cathodes to provide efficient electron injection.