高分子玻璃化转变过程的分子动力学模拟本科教学实验

玻璃化转变是高分子专业教学中的重要内容,转变过程中自由体积的变化和分子链段的运动是理解玻璃化转变的难点。在计算机上使用分子模拟的方法得到三维的可视化图形,可以更直观地观察到自由体积和分子链的变化。提炼近年分子模拟技术在玻璃化转变研究中的最新科研成果,得到既有理论基础又适合本科教学的课程素材。分子模拟可以实现了仪器测试无法达到的超快速升降温,并与仪器测试得到的实验结果相对照,验证了普通实验很难验证的理论观点,从而拓展了本科实验的范围,达到了很好的教学效果。     

气相色谱过程的计算机模拟及操作条件的优化

建立了气相色谱过程的动态数学模型,给出了模型的实用算法,并据此对各种操作条件下的色谱流出曲线进行了动态模拟计算。模拟计算结果表明该模型是有效的,能够用于各种程序控制的色谱过程,可得到色谱分离的优化条件。     

Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities than a specified cutoff sensitivity of 1%. Theactive reactions exert a significant influence on main plasma parameters,such as velocity, temperature, and species concentrations. The sensitivityanalysis for the specified systems shows that two NO reactions, known asZel'dovich reactions (N₂+ONO+N andNO+OO₂+N),⁽¹⁾ are both active in a nitrogenplasma jet. On the other hand, the latter is not active and may be omittedin a nitrogen–hydrogen plasma jet. A nitrogen–hydrogen plasmajet requires contribution of two active charge exchange reactions:N₂+N⁺N⁺ ₂+N andN+H+N+ +H, while only the former is needed in a nitrogen plasmajet. The dissociation reactions are all active in both plasma jets, exceptthe dissociation of OH.     

Lanthanide induced shifts of aromatic 1,2,3-trimethoxy compounds: Conformational analysis of tetrahydrofurofuran-lignans in solution

Summary The solution conformations of 1,4-diaryl-tetrahydro-1H,3H-furo[3,4-c]furans were determined by means of the LIS technique using a modified LIS-simulation program specially designed for the requirements of the aromatic 1,2,3-trimethoxy arrangement as a bidentate coordination site for the NMR shift reagent. The resulting geometries were confirmed by force field calculations (MM2-87) and compared with X-ray derived structures. Reliable data for the conformations in solution allowed a quantitative estimation of the circular dichroism based on the coupled oscillator model.

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Lanthanideninduzierte Verschiebungen von aromatischen 1,2,3-Trimethoxy-Verbindungen: Konformationsanalyse von Tetrahydrofurofuran-Lignanen in Lösung

Zusammenfassung Es wurden mittels der LIS-Technik die Konformationen von 1,4-Diaryl-tetrahydro-1H,3H-furo[3,4-c]furanen in Lösung bestimmt. Dazu mußte ein modifiziertes LIS-Simulationsprogramm entworfen werden, das auf die besonderen Verhältnisse der aromatischen 1,2,3-Trimethoxy-Gruppierung eingeht, welche in den untersuchten Verbindungen als zweizähnige Koordinationsstelle für das NMR-Verschiebungsreagens fungiert. Die resultierenden Geometrien wurden mittels Kraftfeldrechnungen (MM2-87) überprüft und soweit vorhanden auch mit Röntgenstrukturdaten verglichen. Für die Lösungskonformationen wurde eine quantitative Abschätzung des Circulardichroismus auf der Basis des Modells für gekoppelte Oszillatoren durchgeführt.

     

Benefits of X-Ray Spectrum Simulation at low Energies

 There are particular benefits in spectrum simulation for the interpretation of characteristic X-ray peaks below about 2 keV in energy, where peak overlaps, a sloping background and changing detector efficiency make it difficult to measure true peak intensities. Despite these difficulties, we have shown that a useful accuracy of simulation is possible without major revision of the existing theory, allowing the electron microprobe user to compare on-line a measured spectrum with one synthesised from an assumed sample composition. As part of a wider study, we have used a database of X-ray spectra from 150 samples of known composition to confirm the accuracy of simulation over the energy range from 0.28–1.9 keV, finding an RMS error of better than 8%. The database included 181 Kα, Lα and Mα peaks from elements of atomic number 6–77, excited by beam voltages from 5–30 kV. Central to the method is the use of the ratio of (Peak Intensity)/(Total Background Intensity), which allows spectra to be compared from instruments of differing collection efficiency, thereby easing the collection of data over a wide range of conditions. Examples are given to illustrate the use of the simulator in helping to choose the best conditions for analysis, and as an aid in interpreting the spectra so obtained. Both modes of operation are iterative in nature and require a fast and accurate simulator that is easy to use. Further development will be guided by experience in its use.     

三元稀土萃取分离工艺中有效分离系数的研究

本文通过计算机模拟计算,对恒定混合萃取比的三元稀土萃取分离工艺中有效分离系数的变化规律进行了研究,并在串级萃取理论的基础上提出了一种采用有效分离系数确定三元稀土萃取分离工艺参数的方法。     

超离子导体CaF2中的Ca2+亚晶格和F-亚晶格

CaF_2在熔化以前为超离子导体相。一些实验和理论的研究表明,在超离子导体相中,Ca~(2+)仍维持原有的面心立方骨架,而F~-则在Ca~(2+)骨架中运动。早期的分子动力学模拟结果表明Ca~(2+)的均方根位移仅约0.3A,而F~-的扩散系数可达2.6×10~(-5)cm·s~(-1),已是熔盐扩散系数量级。近年来的中子散射实验表明在扩散离子和近邻离子间存在着某种动力学相关。为解释这些事实,新近Gillan的分子动力学模拟表明扩散离子伴随着F~-亚晶格变形,而Kaneko和Ueda的分子动力学模拟则表明扩散离子伴随着近邻离子在同一运动方向的相关运动。进一步的研究尚待进行。八十年代初,Nelson等人提出了描述晶体、非晶和液态中键取向的键球谐函数方法。     

二维卷积在动力学分析中的应用

本文用计算机模拟和二维卷积研究了稀土与间乙酰基偶氮氯膦的显色反应，选择不同的模型参数可描述这类反应的细节，二维卷积则增强对叠合二维谱的分辨。     

Synchrotron X-ray absorption of LaCoO3 perovskite

LaCoO₃ perovskite was prepared at 700°C using citrate precursors. The product was then characterized with X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The powder XRD pattern indicates rhombohedral or its monoclinic I2/a subgroup symmetry. The electronic configuration and the short-range atomic structure of the LaCoO₃ perovskite at room temperature were investigated using synchrotron near-edge X-ray absorption spectroscopy (XANES) and extended X-ray absorption spectroscopy (EXAFS). From the XANES region of the XAS we conclude that Co(III) is at least partly in its intermediate- or high-spin state, which is in accordance with most of the published literature on LaCoO₃ perovskite. The EXAFS region of the LaCoO₃ perovskite spectrum, which up to now was almost not investigated, was simulated satisfactorily for the first two radial structure peaks in terms of the dominant scattering contributions generated with the FEFF8 code and the structural information available from crystallographic data. The best simulation results were obtained with I2/a symmetry. The obtained amplitude reduction factor, zero-energy shift and Debye-Waller factors are useful reference values for data analyses of similar compounds like partly substituted LaCoO₃ perovskite, such as La_1−xCa_xCoO₃ or La_1−xSr_xCoO₃, which are materials of technical interest in catalyst and other applications.     

Study of the Optimal Integrated Control of a Dengue Transmission Model北大核心CSCD

建立了一个登革热在蚊子和人之间传播的模型,引入了Wolbachia、自我保护和杀虫剂三种控制措施,分别从常数控制和时变控制两个方面进行探讨。首先,分析了常数控制对模型基本再生数的影响,研究发现:Wolbachia有助于减小基本再生数,且基本再生数与自我保护和杀虫剂呈负相关。其次,以使得感染数最少且实施成本最低为目标,使用Pontryagin极值原理讨论最优控制。最后,通过数值模拟展示了最优控制的效果。