间二甲苯分子在不同外电场下结构和解离特性研究

间二甲苯是挥发性有机物(VOCs, Volatile Organic Compounds)的关键活性成分,研究其在外电场下的性质十分重要.采用密度泛函理论(DFT),在B3LYP/6-311G++基组水平上对间二甲苯分子进行优化,从分子结构研究了不同外电场(-0.025 a.u.～0.025 a.u.)作用下,间二甲苯分子的总能量,键长,电偶极矩,前线轨道,红外光谱和解离势能面.计算结果表明,沿两甲基中C原子连线方向的电场(-0.025 a.u.～0.025 a.u.)增加时,分子总能量和能隙先增大后减小,电偶极矩先减小后增加.通过计算发现外电场对间二甲苯分子不同键长和不同振动模式的红外光谱的影响均有所不同.间二甲苯分子的解离特性表现为:沿两甲基中C原子连线方向施加强度超过0.047 a. u.的电场时,位于电场增加方向的甲基与苯环之间起连接作用的C-C键断裂.以上计算结果可为利用电场降解间二甲苯提供重要理论参考.     

Hyperchaos,quasi-period and coexisting behaviors in second-order-memristor-based jerk circuit

The European Physical Journal Special Topics - This paper generalizes a second-order-memristor-based jerk circuit, which is achieved by substituting the first-order memristor contained diode-bridge...     

Sommerfeld-type integrals for discrete diffraction problems

Three problems for a discrete analog of the Helmholtz equation are studied analytically using the plane wave decomposition and the Sommerfeld integral approach. They are: (1) the problem with a point source on an entire plane; (2) the problem of diffraction by a Dirichlet half-line; (3) the problem of diffraction by a Dirichlet right angle. It is shown that the total field can be represented as an integral of an algebraic function over a contour drawn on some manifold. The latter is a torus. As a result, explicit solutions are obtained in terms of recursive relations (for the Green’s function), algebraic functions (for the half-line problem), or elliptic functions (for the right angle problem).     

Fully distributed spherical formation tracking control for nonlinear vehicles with spatiotemporal uncertainties and digraphs

Nonlinear Dynamics - This paper addresses the spherical formation tracking control problem of nonlinear vehicles under digraphs, where the dynamics of vehicle contains spatiotemporal uncertainties...     

Morris-Lecar系统中通道噪声诱导的自发性动作电位研究

在生物物理学中, 越来越多的现象是由于分段确定性的动力系统与连续时间马氏过程之间的耦合作用而产生的. 因为这种耦合性, 相关的数学模型更适合取为随机混合系统而不是扩散过程(基于It?随机微分方程). 本文从理论上和数值上研究了在弱噪声条件下无鞍点状态的随机混合Morris-Lecar系统中, 由通道噪声诱导的自发性放电现象. 一个动作电位的初始阶段可视为噪声诱导的逃逸事件, 其最优路径和拟势可由辅助Hamilton系统给出. 由于系统不存在鞍点, 因此可选择虚拟分界线(ghost separatrix)为阈值, 研究噪声诱导的自静息态的逃逸事件. 通过计算在阈值处的拟势, 便可发现其值有一个明显的最小值, 其作用类似于鞍点. 通过改进的Monte Carlo模拟方法, 计算了历程概率分布, 其结果对初始阶段和兴奋阶段的理论解均给出了验证. 此外, 基于前人将拟势等高线作为阈值的另一种选择, 我们对两种阈值取法的优劣性进行了比较. 最后, 本文研究了钠离子和钾离子通道噪声的不同组合对最优路径和拟势的影响. 结果表明: 钾离子通道噪声在自发性放电过程中起主导作用, 且两种噪声强度存在一个最优比例能使总的噪声强度达到最小.      

A microfluidics-dispensing-printing strategy for Janus photonic crystal microspheres towards smart patterned displays

From the implementation point of view, the printable magnetic Janus colloidal photonic crystals (CPCs) microspheres are highly desirable. Herein, we developed a dispensing-printing strategy for magnetic Janus CPCs display via a microfluidics-automatic printing system. Monodisperse core/shell colloidal particles and magnetic Fe₃O₄ nanoparticles precursor serve as inks. Based on the equilibrium of three-phase interfacial tensions, Janus structure is successfully formed, followed by UV irradiation and self-assembly of colloid particle to generate magnetic Janus CPCs microspheres. Notably, this method shows distinct superiority with highly uniform Janus CPCs structure, where the TMPTA/Fe₃O₄ hemisphere is in the bottom side while CPCs hemisphere is in the top side. Thus, by using Janus CPCs microspheres with two different structural colors as pixel points, a pattern with red flower and green leaf is achieved. Moreover, 1D linear Janus CPCs pattern encapsulated by hydrogel is also fabricated. Both the color and the shape can be changed under the traction of magnets, showing great potentials in flexible smart displays. We believe this work not only offers a new feasible pathway to construct magnetic Janus CPCs patterns by a dispensing-printable fashion, but also provides new opportunities for flexible and smart displays.     

Gold-Catalyzed Divergent Ring-Opening Rearrangement of Cyclopropenes Enabled by Dichotomous Gold−Carbenes

The gold-catalyzed ring-opening rearrangement of cyclopropenes affords an efficient route to either polysubstituted naphthols or aryl-substituted furans. Owing to the unique dichotomy of gold−carbenes, this protocol provides a switchable reaction selectivity between naphthols and furans enabled by the use of TFP−Au(MeCN)SbF₆ (tri(2-furyl) phosphine) or PNP(AuNTf₂)₂ (bis(diphenylphosphino)(isopropyl) amine) as catalysts respectively. It is proposed that the gold−carbene intermediate might be involved in the cyclopropene→naphthol rearrangement while the gold-carbocation is more likely to be involved in the cyclopropene→furan rearrangement.     

Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

Fully Chemical Recyclable Poly(γ-butyrolactone)-based Copolymers with Tunable Structures and Properties

Chinese Journal of Polymer Science - The emerging chemical recyclable polymers, such as poly(γ-butyrolactone) (PGBL) and poly((R)-3,4-trans six-membered ring-fused GBL) (P((R)-M)), provide a...