d2,8电子体系共价效应对光谱的影响

在含过渡金属离子的半磁半导体的光学和磁学性质研究中,由于体系的共价性较强,d轨道不再是纯d轨道,而是混合轨道t2g或eg。相应地,需要引入两个共价因子Nt和Ne。建立在混合轨道上的含有共价因子的能量矩阵称为广义能量矩阵。建立了d2,8电子体系的(45×45)阶广义能量矩阵。在广义能量矩阵中,拉卡(Racah)参量A不再是相加常量,同时,d8电子体系不能简单地视为互补的d2空穴体系,因为它们的能量矩阵形式不同。Nt和Ne虽然是属于两个不同轨道的不同的共价因子,但在数值上不能有大的差别,因为考虑进共价效应后,拉卡静电参量A对能级计算有极大的影响。这意味着在通常的光谱拟合中所采用的BCΔ方案是好的近似。以上结论被应用于ZnS∶Ni2 的d-d跃迁谱,计算结果与实验符合。     

同轴线方法测量束流耦合阻抗的有效性分析

根据同轴线方法测量阻抗的原理,用模拟方法讨论了该测量方法的有效性问题。从均匀圆波导和同轴线结构中的电磁场解析分析,说明了该方法有效性问题的起源和基本物理图像,简单回顾其他方法讨论该问题的结论,最后数值模拟分析了同轴线方法测量束流耦合阻抗的有效性,所得主要结论能够对阻抗测量平台的设计提供可靠的依据。     

近地面折射率结构常数的长期测量和统计分析

统计分析了1997～2000年合肥地区一复杂地形处近地面折射率结构常数的测量数据。给出了不同下垫面、不同季节、不同高度上的统计结果。白天强弱依次为6月、5月、4月、9月、1月。白天水面上比草地上小,夜间比草地上大。不论白天还是夜晚,近地面结构常数都随高度递减,且3～10m高的结构常数递减较慢,10～15m高的结构常数递减较快。结构常数随月份的日变化与模式计算结果基本一致。     

大气参数精度对激光传输预估结果的影响

通过对不同情况下参数测量误差导致的到靶激光平均功率密度变化的统计,得到了大气参数精度对激光传输计算结果的影响。风速和气溶胶吸收系数测量误差主要来自热晕效应的影响,热晕越强,对计算结果的影响就越大。强热晕时,风速±(5%～8%)的误差可导致计算结果约±10%的误差;气溶胶吸收权重±(10%～20%)的误差可导致计算结果约 10%的误差。强湍流弱热晕时,大气相干长度±(5%～7%)的误差可导致计算结果约±10%的误差。     

宽频带无源积分器的设计和实验

为获得宽频带的无源积分器,建立了考虑杂散参数的等效电路并进行了电路仿真。结果表明无源积分器的频响上限由杂散参数决定。对于相同结构的积分器,增大RC积分常数,会使杂散参数的影响加剧,导致积分器的高频响应变差。使用同轴结构可以减小电容的杂散电感,提高积分器的带宽。对制作的RC常数为10 μs的同轴式积分器进行了频响实验。实验结果表明：在偏差小于5％的范围内,同轴式积分器带宽为50 kHz～80 MHz。在D-dot电压探头线下标定实验和初级试验平台(PTS)单路样机激光触发开关输出电压测量中,使用该同轴积分器获取的测量波形没有波形畸变和高频干扰。     

Shear-induced band texture of side group liquid crystalline polymers

The shear-induced band texture of conventional end-on fixed side group liquid crystalline polymers (LCPs) has been investigated by using polarizing optical microscopy (POM), small angle light scattering (SALS) and infra-red dichroism techniques. The band spacing is about 1 μm, which increases very slightly on increasing the temperature of shearing and is independent of shearing rate within the range studied. The band texture is not seen to exhibit an interchange of dark and bright bands on rotation of the sample with respect to the polarizer/analyser, but a typical periodical structure is reflected by the SALS patterns of the band texture. The relaxation behaviour of the bands indicates that the band texture formed here is the result of the orderly aligning of domains exhibiting the focal-conic texture, and this is totally different from the case of main chain LCPs where the band texture is substantially an optical effect of the periodic zigzag or sinusoidal structure of parallel aligned microfibrils. Infra-red dichroism and rotating parallel-plate shearing measurements show that the axes of the backbone of the polymer tend to orient in the shearing direction and the end-on fixed mesogenic side groups tend to align perpendicular to the shearing direction.     

A thermodynamic framework to model thixotropic materials

Thixotropic materials are widely used in a variety of industrial applications. The constitutive relations to describe these materials are based on one-dimensional experiments in which the material is subjected to a shear motion and there is no unique methodology to obtain proper three-dimensional models. The path towards generalization to a three-dimensional framework is invariably carried out in a ad hoc manner. Here we propose a three-dimensional model that stems from a general thermodynamic framework that has proved to be quite robust in the development of constitutive relations, namely the application of the second law of thermodynamics together with the maximization of the entropy production. This leads to a constitutive equation that has the same form of a generalized Upper Convected Maxwell equation, if we require that changes of microstructure due to the deformation of each Maxwell element that comprises the model are reversible. Changes in microstructure are governed by a potential that is a measure of the difference between the current structure and the equilibrium structure associated with it. The equilibrium structure associated with the current structure is determined by the current value of stress, considered the main break up agent. We assume that the state of equilibrium would be achieved in a Motion With Constant Stress History, starting from the current stress state, until a steady state where the kinematics is not changing.     

Tuning the mesogenic properties of 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals: the effect of a phenoxy end-group in two sterically equivalent series

Two sterically equivalent series of phenoxy-terminated 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals were synthesised, and their mesogenic properties were characterised by polarised optical microscopy and differential scanning calorimetry (DSC). The phenoxy end-group causes a significant increase in melting point and inhibits – at least partially – the mesomorphism of these materials relative to the parent isomers; in most cases, the broad enantiotropic SmC phase formed by the parent isomers is suppressed by the addition of the phenoxy end-group. However, detailed analyses by small-angle X-ray scattering and monodomain 2D X-ray scattering suggest that these compounds form a SmA phase with a partially intercalated bilayer structure in which the phenoxy end-groups are nanosegregated. Such an intercalated bilayer structure might enable the tuning of smectogenic properties by appropriate substitution of the phenoxy end-groups.     

Electrospinning of poly(lactic acid): Theoretical approach for the solvent selection to produce defect‐free nanofibers

In this study an integrated methodology was proposed for the selection of solvent systems to produce electrospinnable solutions that form defect‐free poly(lactic acid) (PLA) fibers with narrow diameter distributions. The solvent systems were chosen using a thermodynamic approach, combined with electrical and rheological property criteria. More specifically, the three step methodology includes (1) initial choice of solvent by solubility evaluation to meet thermodynamic criteria, (2) electrical properties, that is, conductivity and dielectric constant adjustment by using solvent mixtures to meet electrical property criteria, and (3) critical entanglement concentration (C_e) determination by viscosity measurements, supported by elastic and plastic moduli measurements, followed by concentration adjustment to meet rheological criteria. All three criteria need to be met to ensure defect‐free nanofiber morphology. The methodology was demonstrated using PLA solutions that were characterized in terms of thermodynamic properties, conductivity, surface tension, and viscosity measurements. These data were analyzed and related to the nanofiber morphology and diameter as determined from scanning electron microscopy (SEM). Measurements of the elastic (G′) and the plastic (G″) moduli of PLA solutions showed a sharp increase of G′ at the chain entanglement concentration. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1483–1498     

LiBr分子基态光谱常数和分子常数研究

采用高精度的量子化学从头计算多参考组态相互作用方法和相关一致基, 计算了LiBr分子基态的光谱常数和势能曲线. 为获得更准确的结果, 计算中还考虑了二阶Douglas-Kroll-Hess相对论修正对LiBr分子基态的平衡键长、谐振频率和离解能影响. 将计算得到的势能曲线拟合为Murrell-Sorbie解析势能函数形式, 并进一步计算得到LiBr分子基态的其它光谱常数,ωeχe, αe, Be, D0. 比较发现它们与实验值符合的非常好. 通过求解核运动径向Schrodinger方程, 找到了LiBr分子基态的全部振动态. 还计算了每一个振动态的振动能级、经典转折点和惯性转动常数, 这些结果与已有的实验值一致.