活性氮反应产生激发态卤化氮实验研究

A new method for producing electronically excited nitrogen monohalides NX(b) (X=F,Cl,Br) is reported. The strong emission spectra of NBr(b1Σ+→X3Σ–) are observed when alkyl bromides (CHBr3, CH2Br2, C2H5Br, and C4H9Br) are added to a stream of active nitrogen, generated by a hollow-cathode discharge of N2, in a flowing afterglow system. Some tentative experiments show that the electronically excited NBr(b) is formed by means of metastable N2(A3Σu+) Electronic-to-Electronic energy transfer to NBr(X), which is from the reaction of N(4S) with alkyl bromides. The emission spectra of NCl(b1Σ+→X3Σ–) are obtained when CCl4 or SOCl2 is admitted into a flow of active nitrogen, but neither CHCl3 nor CH2Cl2 addition results in such an emission. It has been proposed that the origin of the excited NCl(b) is an energy transfer from N2 (A) to NCl(X), generated by the reaction of N(4S) with CCl3 (or SOCl2). Similar experiments are also carried out with SF6 as reagent of active nitrogen, or as mixture with N2 in the discharge. By recording fluorescence it was found that excited NF(b) is produced only under discharge through N2/SF6 mixture. The NF(b) state presumably arises from the energy transfer from N2(A) to NF(X), and the latter is generated from the abstraction of fluorine by N(4S) from SF5.     

三氟乙酸对无金属卟啉-苝酰亚胺分子阵列激发态衰变过程的影响

用紫外-可见吸收光谱和荧光光谱研究了CF₃COOH浓度变化对CHCl₃溶液中N-[p-5′-(m^-10′,15′,20′-三苯基卟啉)基]-N′-正十二烷基-3,4:9,10-四羧基二酰亚胺分子阵列(TrPP-MDPTCDI)的光致激发态衰变机理的影响,发现无论激发无金属卟啉还是酰亚胺基元,分子阵列均表现出质子化无金属卟啉生色团的特征荧光发射.对电子结构的分析说明质子化使[H₂²⁺TrPP^*-MDPTCDI]成为各种激发态中相对稳定的物种,因此,未质子化前占主导的从卟啉到酰亚胺基元的光致电子转移衰变途径在质子化后受到有效抑制,激发卟啉生色团(λ=439nm)直接得到[H₂²⁺TrPP-MDPTCDI^*],并以辐射衰变方式回到基态;激发酰亚胺生色团(λ=491nm)得到的[H₂²⁺TrPP^*-MDPTCDI]通过电荷分离态迅速弛豫到[H₂²⁺TrPP^*-MDPTCDI],并辐射荧光,同时伴随少量的从酰亚胺到质子化无金属卟啉生色团的能量转移.     

季戊四醇四硝酸酯晶体能带结构和起爆机理的DFT研究

对季戊四醇四硝酸酯(PETN)晶体进行DFT-B3LYP计算,求得其晶格能为-1.000eV,与实验值相近.前沿能带平坦,表明分子轨道能态受分子晶体场的影响较小.硝基O原子的较大贡献和酯O原子的较小贡献共同组成价带上沿态密度,而空带下沿则由硝基O和硝基N原子共同组成,说明-NO₂基易于接受电子.O-C键的重叠布居数明显比所有其它键的小,加之O-C键鞍点偏离其中点0.022nm,表明该键易于优先异裂起爆.由重叠布居数可知,分子间O…H存在较小的相互作用,[110]方向的撞击将使O…H距离靠近,因而相互作用加强,还使O-C键上的电子向O原子转移,并大大减小该键的重叠布居数,因而促进了该键的异裂.     

噻吩低聚物能级结构的量子化学研究

用量子化学方法计算了系列EDOT低聚物的紫外-可见吸收光谱和前线分子轨道,得到了相应的能级结构参数.与实验值进行对比发现,计算值与实验值具有相同的变化趋势.计算结果表明,通过选择性地改变共轭主链的长度、取代基的位置和取代基的类型,可以规律性地改变化合物光谱性质和能级结构.     

FROM ENERGY IMPROVEMENT TO ACCURACYENHANCEMENT： IMPROVEMENT OF PLATE BENDING ELEMENTS BY THE COMBINED HYBRID METHOD

By following the geometric point of view in mechanics, a novel expression of the combined hybrid method for plate bending problems is introduced to clarify its intrinsic mechanism of enhancing coarse-mesh accuracy of conforming or nonconforming plate elements. By adjusting the combination parameter α∈(0, 1) and adopting appropriate bending moments modes, reduction of energy error for the discretized displacement model leads to enhanced numerical accuracy. As an application, improvement of Adini‘s rectangle is discussed. Numerical experiments show that the combined hybrid counterpart of Adini‘s element is capable of attaining high accuracy at coarse meshes.     

An energy-based anisotropic yield criterion for cellular solids and validation by biaxial FE simulations

The initial yield surface of 2D lattice materials is investigated under biaxial loading using finite element analyses as well as by analytical means. The sensitivity of initial yield surface to the dominant deformation mode is explored by using both low- and high-connectivity topologies whose dominant deformation mode is either local bending or strut stretching, respectively. The effect of microstructural irregularity on the initial yield surface is also examined for both topologies. A pressure-dependent anisotropic yield criterion, which is based on total elastic strain energy density, is proposed for 2D lattice structures, which can be easily extended for application to 3D cellular solids. Proposed criterion uses elastic constants and yield strengths under uniaxial loading, and does not rely on any arbitrary parameter. The analytical framework developed allows the introduction of new scalar measures of characteristic stresses and strains that are capable of representing the elastic response of anisotropic materials with a single elastic master line under multiaxial loading.     

Investigation on thermomechanical fracture in the framework of configurational forces

A configurational force approach is developed for providing a fresh look onto classical aspects of thermomechanical fracture. The theoretical framework is based on the finite deformation and makes no restrictions on the material response. The integral form of configurational force balance at the crack tip is constructed, and the concentrated configurational body force is decomposed into the inertial and internal parts. The energy release rate is evaluated through the generalized second law of thermodynamics applicable to configurational force system. The theoretical investigation shows that the negative of the projection of the internal configurational force concentrated at the crack tip along the direction of crack propagation plays the role of the energy release rate and acts directly in response to crack propagation. This finding enables us to deal with the thermomechanical fracture problems in material space.     

Energy Band Structure of Alq3/TCAQ Heterostructure Complex Film Determinedby Surface Photovoltage Spectroscopy (SPS)

IntroductionOrganic light--emitting diodes (OLEDs) have been extensively investigated since Tanget al. [l] reported a low-voltage high-efficient device in 198712'3]. It has been found that multilayer heterostructures have fascinating advantages in the whole selection of emission color, intensive brightness, high efficiency and relatively low operating voltage['--'J. It is important todetermine the energy band structure of the multilayered film, which will be helpful to interpret the electrol…