过渡金属化合物的CNDO计算VI: NiCp2和Ni2Cp3^+的电子结构

用CNDO法计算了单核金属茂络合物NiCp2和双核金属茂络合物Ni2Cp3^+的电子结构,根据波函数和电子密度等值图的组成分析讨论了二个化合物的成键,在Ni2CP3^+和NiCP2之间进行了比较,指出了它们的化学键特征.     

[Ir(COD)(diphos)Cl配合物活化sp^3 C-H键及其促进CO、CO2插入Ir-C键反应性能的研究

本文利用[Ir(COD)(μ-Cl)]2与双膦螯合配位体之间的反应合成了三个新的配合物[Ir(COD)(diphos)]Cl(diphos=dmpe、depe、dppe),用IR、NMR、电导和元素分析测定了结构.以CH3CN为反应底物分别考察了它们活化sp^3C-H键的能力及其反应规律.在此基础上进一步研究了使CO、CO2插入生成的Ir-CH2CN键的可能性.结果表明:在温和条件下进行这一插入反应是可能的,并用光谱方法证实有相应的含羰基、羧基的金属配合物的生成.     

LiVPO4F电子结构及电化学性质的第一性原理研究

采用密度泛函理论(DFT)结合投影缀加波(PAW)方法,对LiVPO₄F的晶体结构,电子结构和电化学属性进行了研究。从理论上获得了脱Li前后具体的晶格参数的变化。通过对其态密度的计算,发现在放电过程中,V在化合物中呈现离子态,发生+3/+4价态的转变,电子转移主要发生在V原子上;而P原子的状态比较稳定,并不发生大的电子的转移,磷酸根的空间结构也变化不大。同时LiVPO₄F的禁带宽度仅为1.63 eV,说明其在一定情况下具有良好的导电性,有利于放电过程中电子的输运。LiVPO₄F是铁磁相,磁矩为2μ_B,而VPO₄F为反铁磁相。此外,通过计算获得了LiVPO₄F的平均嵌锂电压为4.0 eV。     

Thermodynamic Properties and Relative Stability of Polyhydroxylated Dibenzo-p dioxins Calculated by Density Functional Theory

In this work, partial thermodynamic properties of polyhydroxylated dibenzo-p-dioxins (PHODDs) are calculated by density functional theory (DFT) with the Gaussian 03 program at the B3LYP/6-311G** level. By comparing the total energy Eθ values, it is found that two types of hydrogen bonds exist in PHODDs, one between a hydroxyl and the parent compound (dibenzop-dioxin) with bond energy of approximate 15.7 kJ/mol and the other between two ortho hydroxyl groups with higher bond energy of about 18.3 kJ/mol. Hydrogen bonds have an effect on the conformation stability. On the basis of evaluating the strength of these two types of hydrogen bonds, 75 most stable congeners are ascertained. The relations of calculated thermodynamic parameters (total energy Eθ, zero-point vibrational energy ZPE, correction value of thermal energy Ethθ, heat capacity at constant volume CVθ) with the number and position of hydroxyl substitution (NPHOS) are also discussed. The results show that the NPHOS models can be used to predict the thermodynamic properties for PHODD congeners. In addition, the values of molar heat capacities at constant pressure (Cp,m) from 200 to 1000 K for PHODD congeners are calculated, and the temperature dependence relation of Cp,m is obtained with the least-squares method.     

化学研究2010年第22卷1～6期总目次

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1-取代-2-氨基苯并咪唑衍生物的理论计算及QSAR研究

在B3LYP/6-31＋g(d)计算水平下, 通过运用密度泛函理论(DFT)量子化学方法, 对7种1-取代-2-氨基苯并咪唑衍生物的电子结构特征进行了研究, 获得了它们的电离能、亲合能、化学硬度、化学软度、化学势、电负性、亲电性、分配系数、折射率、极化率、分子体积和分子表面积等参数. 结果表明, 在2-氨基苯并咪唑衍生物的1位引入取代基团, 对化合物的电荷布居和结构性质都有较大的影响|关联了定量结构-活性关系(QSAR), 7种化合物的半数致死量LD₅₀与极化率等有较好的相关性. 这些结果可为1-取代-2-氨基苯并咪唑衍生物的氧化代谢实验研究和毒性机理揭示等提供重要信息.     

《分析化学简明手册》

该书对常用分析方法的基本原理、仪器设备、工作条件和应用领域进行了全面系统的介绍,包括化学基础知识、定性分     

Thermal Decomposition Kinetics of Ethane Halides and Derivatives（C_2H_（6-n）X_n（n = 1～3）;X = F,Cl,Br）：DFT Study and NBO Analysis

A theoretical study of the thermal decomposition kinetics of ethane halides(C2H6-nXn(n = 1～3);X = F,Cl,Br) has been carried out at the B3LYP/6-31++G** and B3PW91/631++G** levels of theory.Among these methods and comparison of activation parameters with available experimental values,the B3PW91/6-31++G** method is in good agreement with the experimental data.The analysis of bond order and natural bond orbital(NBO) charges,bond indexes,and synchronicity parameters suggest the elimination of HX in reactions 1～9(HF:compounds 1～3,HCl:compounds 4～6,and HBr:compounds 7～9) occur through a concerted and slightly asynchronous four-membered cyclic transition state type of mechanism.     

丁酸甲酯单分子解离的非谐振效应

使用MP2/6-311++G（2d,2p）方法和基组,计算了丁酸甲酯单分子解离反应体系详细的势能面。应用RRKM理论,计算了在1000-5000 K的温度范围内的正则系综的速率常数。与此同时,在微正则系综下,我们计算了温度为1000-5000 K对应的能量从451.92到1519.52 kJ·mol^-1的速率常数。计算结果表明反应通道2、4和5的非谐振效应比较明显。因此对于丁酸甲酯单分子解离反应体系来说其非谐振效应是不能忽视的。     

温度对α-Al2O3(0001)表面吸附生长ZnO影响的DFT研究

The adsorption and the growth of ZnO on α-Al2O3(0001) surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials (USP) method based on density functional theory.The average adsorption energy of ZnO at 400, 600 and 800 ℃ is 4.16±0.08, 4.25±0.11 and 4.05±0.23 eV respectively. Temperature has a remarkable effect on the structure of the surface and the interface of ZnO/α-Al2O3(0001). It is found that the Zn-hexagonal symmetry deflexion does not appear during the adsorption growth of ZnO at 400 ℃, and that the ZnO10-10 is parallel with the 10-10 of the α-Al2O3(0001), which is favorable for forming ZnO film with the Zn-terminated surface. It is observed from simulation that there are two kinds of surface structures in the adsorption of ZnO at 600 ℃: one is the ZnO surface that has the Zn-terminated structure, and whose 10-10 parallels the 10-10 of the substrate surface, and the other is the ZnO10-10 //sapphire 11-10 with the O-terminated surface. The energy barrier of the phase transition between these two different surface structures is about 1.6 eV, and the latter is more stable. Therefore,the suitable temperature for the thin film growth of ZnO on sapphire is about 600 ℃, and it facilitates the formation of wurtzite structure containing Zn-O-Zn-O-Zn-O double-layers as a growth unit-cell. At 600 ℃, the average bond length of Zn-O is 0.190±0.01 nm, and the ELF value indicates that the bond of (substrate)-O-Zn-O has a distinct covalent character, whereas the (Zn)O-Al (substrate) shows a clear character of ionic bond. However, at a temperature of 800 ℃, the dissociation of Al and O atoms on the surface of the α-Al2O3(0001) leads to a disordered surface and interface structure. Thus, the Zn-hexagonal symmetry structure of the ZnO film is not observed under this condition