新型功能碳材料的高压截获

高性能功能材料在诸多领域具有广泛的应用前景,是人们一直关注的研究热点。高压可以有效地改变物质的原子间距和成键方式,是获得新型功能材料的重要途径。在碳材料的高压研究中,许多有趣的功能碳材料,如光学透明碳、高强度弹性碳和超硬非晶碳等,已经通过不同的碳前驱体合成。本文简要介绍了作者近年来在低维碳基纳米复合材料高压研究中取得的进展,基于设计的不同低维碳前驱体,高压下截获了具有超硬特性、新型压致共价聚合及发光增强的碳材料。     

Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH₂) and electron-withdrawing (R=NO₂) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L₁)(L₂)]_n ( 1 ) and [Zn(L₁)(L₃)]_n ( 2 ) [L₁=2-(2-pyridyl) benzimidazole (Pbim), L₂=5-aminoisophthalate (Aip), and L₃=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH₂ and NO₂ substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO₂ and NH₂. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.     

High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

零维到三维结构中三核铜自旋阻挫簇单元的磁构关系和反对称交换

量子自旋液体是最近几年刚被人们证实除铁磁体、反铁磁体之外的第三种磁性类型,因其有望解释高温超导的运行机制、改变计算机硬盘信息存储方式而在物理、材料等领域备受关注。自旋阻挫作为量子自旋液体的最小单元可能是解开量子自旋液体诸多问题的钥匙,所以在磁学、电学研究领域再一次成为人们研究的热点。基于文献报道的三核铜配合物[Cu3(μ3-OH)(μ-OPz)3(NO3)2(H2O)2]·CH3OH(1),我们合成了三维金属有机框架配合物{[Ag(HOPz)Cu3(μ3-OH)(NO3)3(OPz)2Ag(NO3)]·6H2O}n(2)(HOPz=甲基(2-吡嗪基)酮肟),并从自旋阻挫的角度对二者磁性质进行对比和详细分析。磁化率数据表明自旋间有很强的反铁磁相互作用和反对称交换。通过包含各向同性和反对称交换的哈密顿算符对两者磁学数据进行拟合并研究其磁构关系,所获最佳拟合参数为:配合物1:Jav=-426 cm^-1,g⊥=1.83,g∥=2.00;配合物2:Jav=-401 cm^-1,g⊥=1.85,g∥=2.00。     

Yield enhancement of elliptical high harmonics driven by bicircular laser pulses

We theoretically investigate the yield enhancement of elliptical high harmonics in the interaction of molecules with bicircular laser pulses by solving the time-dependent Schrödinger equation. It is shown that by adjusting the relative intensity ratio of the two bicircular field components in specific ranges the yield of the molecular high harmonics for the plateau and cutoff regions can be respectively enhanced. To analyze this enhancement phenomenon, we calculate the weights of the electron classical trajectories. Additionally, we also study the ellipticity distribution of harmonics for different intensity ratios. We find that these enhanced harmonics are elliptically polarized, which we mainly attribute to the recombination dipole moment of the major weighted trajectories. These enhanced elliptical extreme ultraviolet and soft x-ray radiations may serve as essential tools for exploring the ultrafast dynamics in magnetic materials and chiral media.     

The Szegö kernel on a class of non-compact CR manifolds of high codimension

We generalize Nagel’s formula for the Szegö kernel and use it to compute the Szegö kernel on a class of non-compact CR manifolds whose tangent space decomposes into one complex direction and several totally real directions. We also discuss the control metric on these manifolds and relate it to the size of the Szegö kernel.     

Meshless acoustic analysis using a weakly singular Burton-Miller boundary integral formulation

The Burton-Miller boundary integral formulation is solved by a complex variable boundary element-free method (CVBEFM) for the boundary-only meshless analysis of acoustic problems with arbitrary wavenumbers. To regularize both strongly singular and hypersingular integrals and to avoid the computation of the solid angle and its normal derivative, a weakly singular Burton-Miller formulation is derived by considering the normal derivative of the solid angle and adopting the singularity subtraction procedures. To facilitate the implementation of the CVBEFM and the approximation of gradients of the boundary variables, a stabilized complex variable moving least-square approximation is selected in the meshless discretization procedure. The results show the accuracy and efficiency of the present CVBEFM and reveal that the method can produce satisfactory results for all wavenumbers, even for extremely large wavenumbers such as k = 10 000.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

基于横向莫尔条纹的自准直测角方法

本文提出了基于横向莫尔条纹的自准直测角方法,用遮光原理分析了莫尔条纹的位移放大作用.并基于该方法搭建了原理光路,得到的莫尔条纹信号稳定且能够满足测量需求.在此基础上对系统进行了定量标定,简化了数据处理步骤,实现了动态测量,系统分辨率达到10″,进一步明确将该方法应用到自准直仪中可以有效提高仪器分辨率.