DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

激光能量对反钙钛矿GaCMn_3薄膜结构与物性的影响

本文采用脉冲激光沉积方法在LaAlO3(001)单晶衬底上制备了反钙钛矿GaCMn3薄膜,通过控制制备过程中脉冲激光的能量,研究了不同激光能量条件对GaCMn3薄膜结构与物理性能的影响.分别利用X射线衍射仪、原子力显微镜、超导量子干涉仪和物理性能测试系统,对所制备的薄膜的晶体结构、表面形貌和磁性、电输运性质进行了研究.结果表明,制备的样品均为具有多个晶面取向的反钙钛矿薄膜,且薄膜结构和物性明显随制备激光能量的变化而变化.当激光能量为450mJ时,制备的薄膜多晶面取向性最弱,结晶性和表面形貌最优良.实验所得的薄膜均表现出顺磁-铁磁-反铁磁相转变,然而转变过程比块材较平缓,同时薄膜的电阻率并未表现出块材中的突变特征,我们推测该现象很可能是由衬底的应力及衬底的晶格膨胀对薄膜反常晶格变化的抑制作用造成的.     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

扩宽OMA-Ⅵ同时谱宽的新方法

OMA－Ⅵ存在同时谱宽窄的缺点，本文用一种新方法大幅度地扩宽了它的同时谱宽，且不降低其系统分辨率，应用效果甚佳。     

具Hardy-Sobolev临界指数的奇异椭圆方程多解的存在性

运用变分方法研究了下面问题-Δpu=μupx(s)s-2u f(x,u),x∈Ω,u=0,x∈Ω,多重解的存在性,其中Ω是一个具有光滑边界的有界区域.     

NiTi合金中马氏体相的低频力学谱研究

我们用最近研制成功的LMA型低频力学谱测试系统对NiTi合金马氏体相进行了在很大频率范围内（0．003～1Hz）的低频等温力学谱和温度谱的测量．我们研究的形状记忆合金NiTi（Ni50．2at％）试样长34mm，直径1mm细丝．经一定热处理，分别在333K．343K和353K做了内耗随频率的变化的测量。实验表明：频率越小，内耗越大，也就是内耗随频率减少而增大。同时我们采用阶梯升温的方法在八个温度下每个温度测量三种频率（1Hz，0．1Hz，0．01Hz）的内耗，结果清楚地表明：不同频率下，内耗峰都出现在372K（99℃）。而且频率越低，峰高越高。这是具有相变峰的特点：相变峰的峰温不随测量频率不同而变化，相变峰高度随频率减少而增大。我们还测量了在1Hz与0．5Hz频率下内耗随温度的变化。本文用马氏体相的位错理论初步讨论了上述实验结果。     

非负定阵元素的扰动和正定完备化

在保持非负定性不变的前提下,本文对矩阵每一元素容许多大的扰动作了进一步的研究, 将本文的结论和C．R．Johnson提出的部分正定阵的正定完备化进行比较,容易发现对已知的正定矩阵求扰动,本文的结论比用C．R.Johnson的正定完备化计算扰动形式上更简单,同时也给出了不同于C．R．Johnson的部分正定阵的正定完备化表示的另外一个公式,推出了这些正定完备化矩阵应具有的若干性质．     

复合体系方法测量液体力学谱

本文介绍了采用复合体系，测量得到凝聚态物质从固态到液态连续变化力学谱的一种新的实验方法。以簧振动为例，给出了解析的计算公式，以及应用条件。通过进一步综合分析，得到具有更广应用范围的近似公式，可以近似应用于其他不同的振动模式，如低频扭摆。应用新的测量方法，给出了典型小分子玻璃材料甘油和碳酸丙稀从玻璃态到液态的力学谱，观察到甘油和碳酸丙稀玻璃化转变、碳酸丙稀的再结晶、熔化和挥发的过程；测量得到挥发过程中水的质量随时间精确变化的曲线。最后，本文给出了新方法的一些应用展望。     

Efficient computation of natural convection in a concentric annulus between an outer square cylinder and an inner circular cylinder

In this work, the natural convection in a concentric annulus between a cold outer square cylinder and a heated inner circular cylinder is simulated using the differential quadrature (DQ) method. The vorticity‐stream function formulation is used as the governing equation, and the coordinate transformation technique is introduced in the DQ computation. It is shown in this paper that the outer square boundary can be approximated by a super elliptic function. As a result, the coordinate transformation from the physical domain to the computational domain is set up by an analytical expression, and all the geometrical parameters can be computed exactly. Numerical results for Rayleigh numbers range from 104 to 106 and aspect ratios between 1.67 and 5.0 are presented, which are in a good agreement with available data in the literature. It is found that both the aspect ratio and the Rayleigh number are critical to the patterns of flow and thermal fields. The present study suggests that a critical aspect ratio may exist at high Rayleigh number to distinguish the flow and thermal patterns. Copyright © 2002 John Wiley & Sons, Ltd.     

Orbital Stability of Solitary Waves for Generalized Zakharov System

In the interaction of laser-plasma the system of Zakharov equation plays an important role.This system attracted many scientists' wide interest and attention.And the formation, evolution and interaction of the Langmuir solutions differ from solutions of the KDV equation. Here we consider the following generalized Zakharov system