A Model Calculation for the Isomerization and Decomposition of Chemisorbed HCN on the Si(100)-2×1 Surface

Ab initio molecular orbital and hybrid density functional theory calculations have been performed to study the adsorption, isomerization, and decomposition of HCN on Si(100)-2×1 using the Si₉H₁₂ cluster model of the surface. The results of our calculations indicate that the HCN can adsorb molecularly without a barrier onto the surface with both end-on (LM1) and side-on (LM2) positions. LM1 can isomerize to LM2 with a small barrier of 8 kcal/mol. The isomerization of LM2 by H-migration from C to the N atom, requires 76 kcal/mol activation energy (c.f. 47.5 kcal/mol in the gas phase) because of surface stabilization. Both HCN(a) and HNC(a) end-on adsorbates were found to dissociate readily, as concluded in our earlier experiment, to produce H and CN adspecies. The computed vibrational frequencies of HCN, CN, and also HCNH adspecies agree reasonably well with those observed experimentally. HCNH was found to be stable, with either the C or the N attaching to the surface.     

ZnO纳米粒子结构对光电量子限域特性的影响

Zn O作为一种宽禁带 (3 .3 6e V)高激子结合能 (60 me V)的半导体材料已引起人们的关注 .Zn O纳米粒子的比表面积较大 ,表面活性较高 ,对周围环境敏感 ,使其成为传感器制作中最有前途的材料[1] ,还在太阳能转换[2 ] 、发光材料[3] 、半导体表面修饰与敏化[4 ] 、纳米电子学以及分子电子学器件[5] 等领域显示出广阔的应用前景 .制约这些应用的关键是 Zn O纳米粒子表面和界面的电子结构和电荷转移行为 ,但有关此方面的报道较少 .本文用溶胶 -凝胶法制备了不同粒径的 Zn O纳米粒子 ,应用表面光电压谱 (SPS)和场诱导表面光电压谱 (FISPS…     

气相中HRnCCH和X(X=H_2O,NH_3)反应机理的理论研究

在CCSD(T)//MP2/aug-cc-pVTZ-pp理论水平上,研究了HRnCCH与大气中H2O及NH3分子反应的机理,反应主要包括HRnCCH与HRnOH及HRnNH2之间的转化、H2O和NH3在HRnCCH中的碳碳三键上的加成反应以及HRnCCH与双分子水反应等.结果表明,HRnCCH与H2O反应生成HCCH和HRnOH及HRnCCH与NH3反应生成HCCH和HRnNH2的能垒分别为54.1和75.2 kJ/mol,而生成HRnCHC(OH)H,HRnC(OH)CH2,HRnCHC(NH2)H和HRnC(NH2)CH2的活化能分别为219.6,220.5,174.4和182.4kJ/mol,此结果表明HRnCCH反应性较弱且是稳态存在的.此外,在HRnCCH与H2O反应中加入单个水分子,仍然生成HRnCHC(OH)H,但反应活化能却降低了96.4 kJ/mol,说明水分子对该反应有明显的催化作用.     

胍盐离子液体捕获CO2温室气体的机理

通过量子力学与分子动力学对胍盐离子液体的模拟表明,胍阳离子与氯负离子之间存在较强的相互作用,其相互作用能约为-109．216kcal／m01．从能量与几何分布可见,两种空间分布方式中最稳定构象为Middle作用模式．径向分布函数也验证了这一结论．C02含量的不断增加并没有对离子液体的结构产生影响,而是被离子液体的空腔捕获．     

Electrochemical Selective Determination of Uranyl Ions Using PVC Membrane Sensor

A UO₂²⁺‐PVC membrane electrode was constructed using 2‐thenoyltrifluoroacetone as ionophore and its electrochemical response performance was characterized. The effect of membrane composition on the electrode performance was studied and best results were obtained using dioctylsebacate as a mediator and potassium tetrakis(4‐chlorophenyl)borate as anion excluder. The optimized UO₂²⁺‐sensor exhibited a Nernstian response with a slope of 29.5±0.5 mV decade⁻¹ over the concentration range 5.0×10⁻⁷−1.0×10⁻¹ mol L⁻¹ at 25 °C with a detection limit of 3.1×10⁻⁷ mol L⁻¹. The optimized electrode showed very good selectivity towards UO₂²⁺ relative to a wide variety of other cations and fast response time. Surface morphology of the optimized membrane electrode at different stages of its development and use was investigated and discussed. Quantum chemical calculations for geometrical optimization of the ionophore were carried out to investigate the interaction between the ionophore and UO₂²⁺ using DFT B3LYP/6‐31++G(d,p) level of theory and the obtained data confirmed the proposed response mechanism. The developed sensor was successfully applied for UO₂²⁺ selective determination in real water samples and the obtained results were compared to those obtained by spectrophotometric method indicating no significant difference.     

Conformational search and spectroscopic analysis of bis-β-d-glucopyranosyl azacrown derivative

1,10-N,N′-bis-(β-d-ureidoglucopyranosyl)-4,7,13-trioxa-1,10-diazacyclopentadecane is a new, recently synthesized compound, which exhibits complexation ability towards drugs. In the present study various theoretical methods, including molecular mechanics, computer simulations, semiempirical and DFT calculations, are applied to find the lowest energy conformers of this molecule in vacuo and in aqueous solution. For the most stable structures the vibrational frequencies as well as the C and H chemical shifts were computed. Along with the theoretical investigation the IR in the KBr discs and the NMR spectra in water and in pyridine were experimentally recorded. It is shown that in the lowest energy structures the two glucosyl units are placed on the same side of the diazacrown ring with their mutual orientations favoring formation of hydrogen bonds. The “open” structure, in which no such hydrogen bonds can be formed, is found to have much higher energy. The computed and measured IR spectra and NMR chemical shifts are compared and discussed in detail. The most stable structures are analyzed with respect to the possible mechanism of complexation of drugs.     

Internally contracted multiconfiguration-reference configuration interaction calculations for excited states

Summary The calculation of electronically excited states with the internally contracted multiconfiguration-reference configuration interaction (CMRCI) method is discussed. A straightforward method, in which contracted functions for all states are included in the basis, is shown to be very accurate and stable even in cases of narrow avoided crossings. However, the expense strongly increases with the number of states. A new method is proposed, which employs different contracted basis sets for each state, and in which eigensolutions of the Hamiltonian are found using an approximate projection operator technique. The computational effort for this method scales only linearly with the number of states. The two methods are compared for various applications.Dedicated in honor of Prof. Klaus Ruedenberg     

基于芘并咪唑的电致发光材料的合成与表征

以芘和咪唑为基本构筑单元,利用"一锅法"合成了一系列芘并咪唑衍生物PyPI,PyTPAI,PyCzI和Pyd-CzI.采用质谱、核磁和元素分析等手段表征了化合物的结构.通过调节与芘并咪唑相连接的共轭基团的种类、大小和空间构型,实现对分子热学性质,分子轨道能级和光电性质的调控.进一步制备了有机电致发光器件,得到了较好的器件性能.     

A C2 Fragment as Four‐Electron σ Donor

The formation and X‐ray structure analysis of the Pt^IV complex [(CH₂C{PPh₂C₆H₄}₂)PtI₂] is reported. The molecule possesses the orthometalated ligand (PPh₃)₂C→CH₂, which serves via its C₂ fragment as an unprecedented four‐electron σ donor.     

Step annealing effects on the structural and optical properties of InAs quantum dots grown on GaAs

The effects of multi-step rapid thermal annealing (RTA) for the self-assembled InAs quantum dots (QDs), which were grown by a molecular beam epitaxy (MBE), were investigated through photoluminescence (PL) and transmission electron microscopy (TEM). Postgrowth multi-step RTA was used to modify the structural and optical properties of the self-assembled InAs QDs. Postgrowth multi-step RTAs are as follows: one step (20 s at 750 °C); two step (20 s at 650 °C, 20 s at 750 °C); three step (30 s at 450 °C, 20 s at 650 °C, 20 s at 750 °C). It is found that significant narrowing of the luminescence linewidth (from 132 to 31 meV) from the InAs QDs occurs together with about 150 meV blueshift by two-step annealing, compared to as-grown InAs QDs. Observation of transmission electron microscopy (TEM) shows the existence of the dots under one- and two-step annealing but the disappearance of the dots by three-step annealing. Comparing with the samples under only one-step annealing, we demonstrate a significant enhancement of the interdiffusion in the dot layer under multi-step annealing.