Theoretical exploration of structure-reactivity relationships in organometallic chemistry: butadiene insertion into the organyltransition-metal bond and conversion of the allyltransition-metal fragment in the [Ni(η-Cp)(η-phenyl)(η-butadiene)] complex

We have theoretically examined the reaction course of the butadiene insertion into the arylNi^II bond in the [Ni^II(η⁵-Cp)(η¹-phenyl)(η²-butadiene)] complex (1), by employing a gradient-corrected DFT method. Critical elementary processes have been scrutinized, viz. monomer insertion, rotational allylic isomerization and allylic η¹-σ→η³-π rearrangement. The first mechanism suggested by Lehmkuhl et al. was refined and supplemented with important details. The critical factors that determine the generation of anti-η³- and syn-η³-allyl isomers of the [Ni^II(η⁵-Cp)(1-benzyl-allyl)] product have been elucidated. This let us to rationalize the experimentally observed, almost exclusive formation of the anti-η³-allyl isomer. Butadiene preferably inserts in η²-mode into the η¹-phenylNi^II bond, initially giving rise to the η¹(C³)-allyl product species, 3σ. The direct formation of the η³-allyl product species, 3π, along the alternative path for η⁴-butadiene insertion, however, is found to be almost entirely disabled kinetically. The thermodynamically favorable η²-trans form of 1 is also shown to be more reactive in accomplishing CC bond formation. Species 3σ is indicated to be a metastable intermediate, occurring in an appreciable stationary concentration. Its respective anti and syn isomeric forms are likely to be in equilibrium, due to the facile rotational isomerization. The subsequent allylic rearrangement into the thermodynamically strongly favorable η³-allylNi^II coordination mode is shown to be the crucial elementary step that discriminates which of the isomeric η³-allyl forms is preferably generated. The higher reactivity of the anti isomer in this process decisively determines the almost exclusive formation of the anti-η³-allyl product species under kinetic control. The requirement of elevated temperatures for the anti-η³-allyl→syn-η³-allyl isomerization to occur, as revealed from experiment, is attributed to the pronounced thermodynamic stability of the η³-allylNi^II coordination.     

分块镜扇形子镜驱动点位置优化计算

在光学综合孔径共相位检测微调系统中,分块镜子镜三自由度微动调节机构通常采用3个并联的微位移致动器来驱动各子镜,使单个分块镜具有独立的姿态调整能力,从而实现了光学共相位误差的纳米级精确校正。以理论力学原理作为切入点展开了分析,针对微动机构的稳定性、tilt-tip调节灵敏度等,根据所给定几何参数的子镜三驱动点位置对其进行了优化计算。经数学建模和仿真计算,得到了定参数子镜的三驱动点最佳位置坐标,进而归纳出了普遍适用的优化评价方法。     

Quantum Information Entropies on Hyperbolic Single Potential Wells

In this work, we study the quantum information entropies for two different types of hyperbolic single potential wells. We first study the behaviors of the moving particle subject to two different hyperbolic potential wells through focusing on their wave functions. The shapes of these hyperbolic potentials are similar, but we notice that their momentum entropy densities change along with the width of each potential and the magnitude of position entropy density decreases when the momentum entropy magnitude increases. On the other hand, we illustrate the behaviors of their position and momentum entropy densities. Finally, we show the variation of position and momentum entropies Sx and Sp with the change of the potential well depth u and verify that their sum still satisfies the BBM inequality relation.     

基于永磁体间的磁性负刚度的分析与优化

为了有效地降低磁性负刚度结构的非线性程度,从简单三磁体结构出发,引入新型负刚度结构模型——五磁体对称结构,运用MATLAB建立新型负刚度结构的磁力学模型并应用Ansoft Maxwell进行仿真验证.研究永磁体间的相对位置参数对五磁体对称结构的负刚度曲线走势的影响,在微幅振动下对基于磁引力的负刚度曲线拟合后使用谐波平衡...     

偏轴双腔互比型腔式束流位置监测器

 提出一种利用偏轴双腔来监测电子束位置的新方法,根据谐振腔归一化分流阻抗参数分析了其工作原理和主要特性。偏心束流在偏轴谐振腔中激发出较强的偶极模TM₁₁₀信号,根据两腔输出的偶极模信号幅度比可直接测量束流的中心偏移量。偶极模信号幅度变化反映了束流的偏移方向,省去了鉴相工作,简化了前端接收电路的的设计,基模抑制问题已被解决。利用MAFIA和HFSS软件对本征模进行仿真,并分析了模式耦合特性,仿真结果验证了新结构的可行性。     

酚醛树脂中亚甲基对热降解的影响

将固化后的酚醛树脂在不同温度下进行热处理,对固化后的样品进行热重分析,对热处理后的试样进行傅立叶红外光谱分析.实验结果表明,酚醛树脂的热降解与亚甲基的取代位有关.酚醛树脂中的亚甲基分两个阶段进行热解降,350~450℃的温度区间主要是部分邻-邻(o-o′)位亚甲基和邻-对(o-p)位亚甲基的分解,400~620℃温度区间为对-对(p-p′)位亚甲基的分解,p-p′位亚甲基比o-o′位亚甲基的起始热分解温度高50℃左右.     

航天器对接相对位置姿态自主测量方法研究

航天器间相对位置姿态的准确测量是实现自主自动对接的先决条件。将三圆标志靶安装在目标航天器上;追踪航天器用数码相机对靶拍照。设计了亚像素处理方法实时处理数字照片,可精确测定圆心像点位置和特征直径的像长;用其作为基本特征参数,基于透视投影原理,建立了求圆心物空间坐标的公式,求出靶面的平面方程,可用来求两航天器间的相对位置姿态参数和实时标定相机的可变参数。计算机仿真结果表明,测距为2m时,测圆心像点位置的误差小于0.03个像素,测距误差小于1mm,测姿态角的误差小于0.01°。该方法也适用于无人直升飞机定点着陆时自主测量其相对位姿参数。     

超图结构上合作博弈的赋权Position值

在合作博弈的一般模型中总是假设所有联盟都能形成。不过,在实际中由于受到一些因素的制约,有些联盟是不能形成的。基于此,Myerson提出了具有图通讯结构的合作博弈。Myerson值和Position值是超图博弈上的两个重要分配规则。2005年,Slikker给出了在图博弈上Position值的公理化刻画。但超图博弈上Position值的公理化刻画一直悬而未决。本文通过引入“赋权平衡超边贡献公理”,并结合经典的“分支有效性”,提出了超图博弈上赋权Position值的公理化刻画。作为推论,解决了超图博弈上Position值的公理化刻画问题。     

改变飞艇重心位置控制纵向运动

本文针对目前平流层飞艇的运动控制效率较低的问题,重点研究了改变平流层飞艇重心的轴向位置来控制飞艇的纵向运动。首先讨论了考虑飞艇重心位置的力和力矩平衡,并利用德国斯图加特大学风洞试验的数据,进行了算例分析。然后和常用的升降舵控制进行效率比较,得出了在空气密度较低的平流层采用改变重心位置比舵面控制具有优越性的结论。最后提出了改变飞艇重心位置的方法。     

监管技术巨头：技术力量作为市场支配地位认定因素之再审视

如何有效规制技术巨头已然成为当前《反垄断法》修订的重要任务。技术力量虽然作为传统的市场支配地位认定要素,但长期以来呈现被虚置化的客观状态,致使技术巨头市场支配地位的认定难度增大,技术力量自身的传导效应被显著低估。数字技术对市场竞争的影响异于以往,其通过平台、数据、算法的数字市场三维结构框架影响生产与交易的全过程。技术与三维结构结合所形成的技术力量极为强大,超越了以控制价格为主的传统市场力量,结合社会与资本力量形成了更牢固的市场固化结构。在判断技术巨头的市场支配地位时,亟需发挥技术力量作为非价格型认定要素的重要作用。应当摒弃虚置技术力量作为市场支配地位认定要素的固有症结,提高技术力量在认定市场支配地位时所占权重,回归结构性视角,妥善防范技术巨头无序扩张。