二甲基亚锗基锗烯与乙醛生成螺锗杂环化合物反应机理的密度泛函理论研究

用B3LYP/6-31G*方法研究了单重态二甲基亚锗基锗烯(Me₂Ge=Ge:)与乙醛环加成反应的反应机理,根据该反应的势能面可以预言,该反应有一条主反应通道. 该反应所呈现的反应规律为：两反应物通过[2+2]环加成反应首先生成了一锗杂四元环锗烯,由于该锗杂四元环锗烯中Ge:原子的4p空轨道与乙醛的?轨道形成了π→p授受键,从而使锗杂四元环锗烯进一步与乙醛结合生成了一中间体. 由于该中间体中的Ge:原子在过渡态之后发生了sp³杂化,从而使该中间体经过渡态异构化为了一螺锗杂环化合物. 该研究结果从理论上揭示了单重态二甲基亚锗基锗烯(Me₂Ge=Ge:)与乙醛环加成反应的反应机制,奠定了亚锗基锗烯(H₂Ge=Ge:)及其衍生物(X₂Ge=Ge:, X=H, Me, F, Cl, Br, Ph, Ar?)与非对称性π键化合物环加成反应的理论基础.     

丙烯腈-尿素包合物的形成过程及特征

利用差示扫描量热法(DSC)和X射线衍射(XRD)研究了在不同丙烯腈/尿素投料比情况下的丙烯腈-尿素包合物的形成过程和组成. 实验结果表明DSC是一种研究包合物的客主比及分解热的有效方法. 测定了丙烯腈-尿素包合物的客主比和分解热分别为1.17和5361.53 J/mol. 同时发现丙烯腈-尿素包合物的形成依赖于冷冻时间,在足够长的冷冻时间之后丙烯腈-尿素包合物的组成达到稳定状态. 实验结果表明,丙烯腈分子可能是采用堆叠的方式排布在尿素晶道结构中. XRD结果表明只要丙烯腈分子进入尿素晶格中,丙烯腈-尿素包合物的结构便形成了,并且这种结构与形成过程终了时的结构是一致的. 只要丙烯腈是足量的,包合物中的丙烯腈分子排列会随冷冻时间的延长而增长,直到尿素的晶道结构被丙烯腈分子填满.     

Magnetic transition and large reversible magnetocaloric effect in EuCu1.75P2 compound

The magnetocaloric effect(MCE) in EuCu1.75P2 compound is studied by the magnetization and heat capacity measurements.Magnetization and modified Arrott plots indicate that the compound undergoes a second-order phase transition at TC ～ 51 K.A large reversible MCE is observed around TC.The values of maximum magnetic entropy change(-△SxMma) reach 5.6 J·kg-1·K-1 and 13.3 J·kg-1·K-1 for the field change of 2 T and 7 T,respectively,with no obvious hysteresis loss in the vicinity of Curie temperature.The corresponding maximum adiabatic temperature changes(△Tadmax) are evaluated to be 2.1 K and 5.0 K.The magnetic transition and the origin of large MCE in EuCu1.75P2 are also discussed.     

ICF靶丸装配误差检测

针对激光惯性约束聚变装置中靶丸装配误差检测困难、要求精度高的特点,研制了一套用于微靶装配参数检测的测量系统。提出了一种基于激光与CCD的复合式测量方法,建立了二者数据融合的数学模型,通过标定空间位置关系有效地把二者的测量数据融合到同一个坐标系中,从而实现了高精度三维测量。分两种情况讨论了靶丸装配误差的检测方法。实验结果验证了这两种方法的可行性,并比较了两种方法的测量精度,其极限测量误差均不超过3 m。     

Phase coexistence in NaZn13-type LaFe11.4Al1.6C0.02 compound

In NaZn₁₃-type LaFe_11.4Al_1.6C_0.02 compound, a signature of weak ferromagnetism is observed at ∼100 K under a low field by ac magnetic-susceptibility and electrical-resistivity measurements, implying the coexistence of ferromagnetic (FM) and antiferromagnetic (AFM) phases. The hysteresis in isofield magnetization curves and large magnetic relaxation demonstrate the metastability of the magnetic state in the AFM-FM transition region. The variations of magnetization with temperature, time and field show distinct step-like behaviors, which is probably attributed to the discontinuous growth of ferromagnetic cluster in antiferromagnetic matrix.     

Substituent effects on gas‐phase homolytic Fe–N bond energies of m‐G‐C6H4NHFe(CO)2(η5‐C5H5) and m‐G‐C6H4N(COMe)Fe(CO)2(η5‐C5H5) studied using density functional theory methods

One of the most fundamental properties in chemistry is the bond dissociation energy, the energy required to break a specific bond of a molecule. In this paper, the Fe–N homolytic bond dissociation energies [ΔH_homo(Fe–N)'s] of 2 series of (meta‐substituted anilinyl)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄NHFp ( 1 )] and (meta‐substituted α‐acetylanilinyl)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄N(COMe)Fp ( 2 )] were studied using density functional theory methods with large basis sets. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G is NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that Tao‐Perdew‐Staroverov‐Scuseria, Minnesota 2006, and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔH_homo(Fe–N)'s. The ΔΔH_homo(Fe–N)'s ( 1 and 2 ) conform to the captodative principle. The polar effects of the meta‐substituents show the dominant role to the magnitudes of ΔΔH_homo(Fe–N)'s. σ_α· and σ_c· values for meta‐substituents are all related to polar effects. Spin‐delocalization effects of the meta‐substituents in ΔΔH_homo(Fe–N)'s are small but not necessarily zero. RE plays an important role in determining the net substituent effects on ΔH_homo(Fe–N)'s. Insight from this work may help the design of more effective catalytic processes.     

光学仪器胶粘剂应用现状及进展

本文是在对国内光学零件加工及光学仪器产品胶粘剂的应用现状与研究动态的调研基础上，结合作者的工作，综合介绍了光学零件加工过程中工艺用粘接材料与工艺材料用树脂结合剂；光学零件、光学分划元件、光学偏振元件、光学塑料元件等的胶合用光学胶；光学仪器产品结构用结构胶及非结构胶；光学仪器产品及部件用密封胶等的应用现状及其进展概况     

三组元乳化液雾化特性的研究

采用Malvern粒度仪对柴油、甲醇和水三组元乳化液的雾化特性进行了研究。实验发现:对于压力雾化喷嘴来说,本文所涉及的乳化液由于粘度高于纯柴油,因此雾化效果比纯柴油差,而且喷射压力、乳化剂的粘度和乳化液的组份对乳化液的雾化特性具有显著的影响。随着喷射压力的升高,乳化液喷雾粒径将随之减小;若乳化液中柴油的含量(柴油不少于50％)降低,乳化液的雾化粒径将随之增加;若采用高粘度的乳化剂,相应乳化液喷雾的粒径也大。     

重离子熔合反应与双核模型

简单介绍了兰州-北京-吉森合作组对合成超重核的重离子反应进行的初步研究。研究的重点是熔合阶段的反应机制。在原有双核模型的基础上做了一些改进,把耗散相对运动过程与核子转移过程耦合起来,从更微观的角度来描写双核系统向全熔合复合核的演化。在双核过程中的每一步求解主方程,不对驱动势做谐振子近似。同时,还探讨了原子核形变与相对取向对驱动势的影响,存活几率与复合核蒸发中子的奇偶效应,以及入射道中原子核非弹性激发对俘获截面的影响等。In recent years, the Lanzou-Beijing-Giessen collaboration has studied the heavy ion reactions which are lead to the formation of super-heavy nuclei. The study emphases the mechanism of the fusion stage of the reactions. Based on the so called Di-nuclear System Model, some improvements have been made. The main points are the coupling of the dissipation of relative motion energy, angular momentum with nucleon transfer, and solving the Master equation in every step of the nucleon transfer with exact driving potentials, in order to describe the evolution of the system more microscopically. At the same time, we also discussed the effects of nuclear deformation and their relative orientation on the driving potentials, and studied the survive probability of the compound nuclei and its old-even effects, as well as the influence of inelastic excitations of nuclei in entrance channels to the capture cross sections.     

Pixel-by-pixel analysis of DCE MRI curve patterns and an illustration of its application to the imaging of the musculoskeletal system

Dynamic contrast enhanced (DCE) MRI is a widespread method that has found broad application in the imaging of the musculoskeletal (MSK) system. A common way of analyzing DCE MRI images is to look at the shape of the time-intensity curve (TIC) in pixels selected after drawing an ROI in a highly enhanced area. Although often applied to a number of MSK affections, shape analysis has so far not led to a unanimous correlation between these TIC patterns and pathology. We hypothesize that this might be a result of the subjective ROI approach. To overcome the shortcomings of the ROI approach (sampling error and interuser variability, among others), we created a method for a fast and simple classification of DCE MRI where time-curve enhancement shapes are classified pixel by pixel according to their shape. The result of the analysis is rendered in multislice, 2D color-coded images. With this approach, we show not only that differences on a short distance range of the TIC patterns are significant and cannot be appreciated with a conventional ROI analysis but also that the information that shape maps and conventional standard DCE MRI parameter maps convey are substantially different.