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。     

噪声模态单元预判的经验模态分解脉冲星信号消噪

为了改善脉冲星辐射脉冲信号的消噪效果, 提出了一种基于噪声模态单元预判的经验模态分解(EMD) 消噪声方法. 该方法首先利用EMD将含噪辐射脉冲信号分解为一组内蕴模态函数(IMF), 根据IMF系数的统计特性采用局部均方误差准则进行噪声模态单元预判, 并将噪声模态单元置零; 然后对噪声模态单元预判处理后的IMF以模态单元为基本单位进行最优比例萎缩消噪, 从而达到抑制噪声、保留信号的目的. 实验结果表明: 与Sure Shrink小波阈值法、Bayes Shrink小波阈值法和EMD模态单元比例萎缩法相比, 基于噪声模态单元预判的EMD消噪方法可以更有效地去除脉冲辐射信号中的噪声, 同时更好地保留信号突变处的细节信息特征, 在信噪比、 均方误差、峰值相对误差、峰位误差和相位误差等方面都有一定程度的改善. 关键词： 脉冲星信号消噪 经验模态分解 噪声模态单元预判 局部均方误差     

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.     

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.     

Numerical study of charge ordering in NaxCoO2

A simple microscopic model of charge ordering in the Na_xCoO₂ system is presented. The model takes into account the interplane interactions between the ordered Na ions and d electrons from the CoO₂ layers as well as the nearest-neighbor intraplane Coulomb interactions between d electrons. It is shown that a driving force of charge ordering in the CoO₂ layers is the interplane interaction that alone is able to describe various types of inhomogeneous charge ordering (e.g., the striped phases) as well as to predict correctly the conducting properties of the system.     

5-呋喃基-1-苯并噻唑基吡唑啉类荧光化合物的合成及光谱分析

吡唑啉衍生物具有高的蓝色荧光,并且具有高量子效率,很易于用作发光材料中电子传输层。依据Schellhammer经验中化学结构与荧光性关系,在吡唑啉的1-位引入了苯并噻唑基,3-位引入苯基衍生物,使其具有荧光性,5-位引入呋喃基作为助色团,可使荧光波长红移,增加荧光性。文章设计并合成了六种5-位引入呋喃基苯并噻唑吡唑啉类荧光化合物,通过红外光谱、荧光光谱、1HNMR、元素分析对合成的化合物进行了表征,表明这类化合物具有良好的荧光性,其最大发射波长在440～460 nm之间,经过分析得知其荧光强度的大小与衍生物中不同的取代基有关。