H-ZSM-5分子筛上的乙烯二聚反应机理的理论计算研究

应用分子力学和量子力学联合的ONIOM2(B3LYP/6-31G(d,p):UFF)计算方法研究了H-ZSM-5分子筛上乙烯二聚反应的机理. 用40T簇模型模拟ZSM-5分子筛位于孔道交叉点的酸性位,对乙烯二聚过程的分步反应和协同反应两种机理进行了考察. 对于分步反应机理,乙烯分子首先通过π-氢键作用在酸性位形成稳定的吸附络合物,再进一步发生质子化并生成乙醇盐中间体,随后乙醇盐与第二个乙烯分子发生碳-碳键结合形成丁醇盐产物. 第一步质子化和第二步碳链聚合的活化能分别为152.88和119.45 kJ/mol, 表明乙烯质子化反应为速控步骤. 对于协同反应机理,乙烯质子化、碳-碳键和碳-氧键生成同时进行,生成丁醇盐,反应的活化能为162.30 kJ/mol, 略高于分步反应机理中的速控步骤. 计算结果表明这两种反应机理之间存在相互竞争.     

基于联合变换相关器的像移测量仿真分析

对基于联合变换相关器的像移测量数学原理进行了说明,介绍了面阵CCD的安装位置以及输入图像的获取方法,分析了低信噪比输入图像、相对转动位移对测量精度的影响。应用MATLAB对输入图像进行傅里叶变换得到联合功率谱,对二值化处理的功率谱进行傅里叶变换得到相关输出,用质量中心算法计算出像移量。分析得出,输入图像信噪比大于5dB,测量均方误差小于0.05像素;输入图像相对转动位移在0.1°的范围内,转动位移对测量精度和峰噪比的影响可以忽略不计。综合分析表明像移测量均方误差小于0.05像素。     

Negative thermal expansion in NbF_3 and NbOF_2:A comparative theoretical study

Thermal expansion control is always an obstructive factor and challenging in high precision engineering field. Here,the negative thermal expansion of Nb F_3 and Nb OF_2 was predicted by first-principles calculation with density functional theory and the quasi-harmonic approximation(QHA). We studied the total charge density, thermal vibration, and lattice dynamic to investigate the thermal expansion mechanism. We found that the presence of O induced the relatively strong covalent bond in Nb OF_2, thus weakening the transverse vibration of F and O in Nb OF_2, compared with the case of Nb F_3.In this study, we proposed a way to tailor negative thermal expansion of metal fluorides by introducing the oxygen atoms.The present work not only predicts two NTE compounds, but also provides an insight on thermal expansion control by designing chemical bond type.     

H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

甲醇制烯烃(MTO)作为一条由煤、天然气和生物质等含碳资源制备重要有机化学品的非石油路线,近年来备受关注.作为MTO催化剂,分子筛的骨架拓扑结构和酸性质对于其催化活性、反应路径和产物分布等具有重要的影响.H-ZSM-5分子筛是一种典型的MTO反应催化剂,酸位可以分布在MFI拓扑结构的直孔道、正弦孔道和交叉位点处.虽然目...     

一种计算液接电势的新方法*

依据液接电势达稳态时通过边界层的净电荷为零这一思想,提出了一种计算液接电势的新方法。对于3类液接电势的计算,特别是Lewis-Sargent公式与Henderson方程的推导,思路清晰易懂,避免了过往液接电势计算方法存在的一些问题。本文所提出的方法能够为液接电势相关内容的教学提供借鉴。     

松香中枞酸型树脂酸的MNDO研究

应用半经验MNDO量子化学计算方法确定了松香中4种枞酸型树脂酸的优化几何构型及相对能量，据此对该类树脂酸分子的构象及相对稳定性作了分析与预测，并与已知的实验结果作了对比。     

酸碱型体分布系数计算的新方法

基于代数法,借助浓度对数图建立了一种计算酸碱型体分布系数的新方法。用该方法计算酸碱型分布系数,仅需对ＰＨ值及相关ＰＫａ值作加减衣简单的对数和指数运算,计算结果与代数法吻合。     

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.     

双氮桥联1,10-菲咯啉大环化合物分子构型的从头算研究

应用规范不变原子轨道法(GIAO)在RHF/6-31G**和B3LYP/6-31G**水平上计算了质子化双氮桥联1,10-菲咯啉大环化合物(H4HAPP2+)C2h和C2h构型的1HNMR,并用TDDFT法计算了H4HAPP2+电子光谱.结果表明,B3LYP/6-31G*优化的C2h构型为较优构型,经谐振频率验证无虚频,C2h构型是H4HAPP2+合理的对称性构型.     

An Ab Initio Study of N_2O Decomposition on MgO Catalyst

Nl0isalwaysusedasoxidantinalotofoxidativecatalyticprocesses,suchastheoxidativecouplingofmethane(0CM),oxidativedehydr0genationofalkanesands0on,becauseitdecomPosestoprovideOadspeciesonmetal0xidecatalystsandleadstothespecificoxidativeselectivity.Forexample,itwasf0undthatf0rOCMreacti0nonMgOandLougOcatalystS,thereactiontemPeraturerequiredislowerwhenoneusesN20asoxidantthanusing0,'.TheunderstandingofN20dec0mposihon0nmetal0xidecatalystsandthepropertiesofthereIevant0adspeciesshouldbeagoodstarting…