Effect of Molecular Weight on Liquid Crystal Photoalignment by Photosensitive Polyester Containing Thrifluoromethyl Moieties

We investigate the liquid-crystal （LC） alignment direction on photoalignment films formed from photosensitive polyester containing thrifluoromethyl moieties （PPDA） with various molecular weights by crossed polarized optical microscopy. It is found that LC alignment behaviour changes with molecular weight of PPDA. The LC alignment on PPDA irradiated films with the highest molecular weight is homogeneous, while those with low and intermediate molecular weights are homeotropic. However, surface morphologies show weak dependence on molecular weight. The surfaces are smooth and there is no clear morphological anisotropy on these aligned films observed by an atomic force microscope. The surface energies of the irradiated films are also measured by using an indirect contact-angle method where both surface energy and its polar component, increase with increasing molecular weight. Different polar surface energies can be considered as a main reason for different alignment characteristics.     

OH+C2H3F的反应机理及产物支化比反应的理论研究

本文对HOC₂H₃F可能解离通道的势能面进行从头算CCSD(T)/CBS//B3LYP/6-311G(d,p)计算,同时对速率常数进行Rice-Ramsperger-Kassel-Marcus计算. 生成主要产物CH₂CHO+HF最有利的反应途径是OHC₂H₃F→i2→TS14→i6→TS9→i3→TS3→CH₂CHO+HF,其中速率决定步骤是HF通过TS11从CO桥接位置解离,能量比反应物高3.8 kcal/mol. 借助中间态TS14,F原子从C_α迁移到C_β位置生成CH₂O+CH₂F,然后通过中间态TS16,H从O迁移到C_α位置;通过中间态TS5,C-C键断裂生成产物,其能量比反应物低1.8 kcal/mol,比TS11低4.0 kcal/mol.     

基于全息液晶/聚合物光栅的分布反馈式激光器的波长调谐特性研究

首先制备了不同周期的染料掺杂全息液晶/聚合物光栅并进行激光抽运实验, 得到了激光器的调谐曲线,确定了激光器在574 nm到685 nm的谱带里均可以实现激光输出, 即激光器具有110 nm左右的可调谐范围. 之后, 通过温控仪控制样品的温度, 对周期为610 nm的染料掺杂全息液晶/聚合物光栅进行激光抽运, 探测不同温度下的输出激光光谱, 观察到随着温度由20℃升高到65℃, 激光器的中心波长由627.9 nm减小到623 nm, 产生了4.9 nm的波长蓝移.     

Rotational viscosity of a liquid crystal mixture: a fully atomistic molecular dynamics study

Fully atomistic molecular dynamics (MD) simulations at 293, 303 and 313~K have been performed for the four-component liquid crystal mixture, E7, using the software package Material Studio. Order parameters and orientational time correlation functions (TCFs) were calculated from MD trajectories. The rotational viscosity coefficients (RVCs) of the mixture were calculated using the Nemtsov--Zakharov and Fialkowski methods based on statistical-mechanical approaches. Temperature dependences of RVC and density were discussed in detail. Reasonable agreement between the simulated and experimental values was found.     

非接触式测量电控喷油器针阀响应特性的研究

为了精确测量电控喷油器针阀的运动规律,以汽油机低压电磁阀喷油器为研究对象,采用了霍尔传感器测量电控喷油器针阀响应时的电磁阀电流信号,并引入高速摄像对整个喷雾过程进行同步观察的方法。通过对比分析针阀运动时的喷油器电路中电流信号变化规律和高速摄像系统观察到的实时喷雾图像之间的对应关系,表明针阀的运动响应和霍尔元件传感器的输出电压存在确定的关系,并对针阀运动引起的磁路变化、电流变化进行了理论分析验证。在无需对喷油器进行任何改造的前提下,设计了一套电控喷油器针阀开启及落座滞后时间的测量系统,实现了对电磁喷油器喷油时针阀运动的实时、精准测量。     

楔形盒染料掺杂胆甾相液晶激光器研究

设计制作了楔形盒掺杂激光染料PM580的胆甾相液晶器件, 研究了激光辐射行为. 在楔形液晶盒中出现了一系列与楔棱平行的向错线和不同规则形状的晶畴, 胆甾相液晶形成了平面态排列. 采用固体Nd:YAG倍频532 nm 波长激光作为抽运光, 获得调谐精度约1 nm, 调谐范围约17 nm的一维波长可调谐激光器. 楔形盒中, 液晶扭曲力与取向膜表面锚定力相互平衡的过程中胆甾相液晶螺距伸张, 光子禁带位置移动, 从而调谐光子禁带边沿出射激光波长. 关键词： 胆甾相液晶 楔形盒 激光辐射     

Influence of molecular mass on the liquid crystal alignment of photosensitive fluorinated polyester films

Photosensitive fluorinated polyesters (polymer-n) of varying molecular mass M _n (number-average molecular mass) were synthesized. The thin films formed from polymer-n samples could induce liquid crystal (LC) alignment after irradiation by linearly polarized ultraviolet light. The LC alignment direction on the irradiated films was investigated in detail by linearly polarized infrared spectroscopy and polarizing optical microscopy. It was found that LC alignment behaviour changed with change in the molecular mass of polymer-n: irradiated films with lower or higher M _n induced homeotropic or homogenous alignment, respectively. There was no clear morphological anisotropy in these aligned films, as observed by atomic force microscopy. The surface energies of the irradiated films were also measured using the indirect contact angle method, where both surface energy and its polar component increased with increasing M _n. The variation in M _n could be considered as a main reason for varying alignment behaviour.     

Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe₁©SiC₂), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH₂ intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe₁©SiO₂ and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism.     

向列相液晶nCB(4-n-alkyl-4'-cyanobiphenyls,n=5-8)的旋转黏度及其奇偶效应的分子动力学模拟

在全原子力场模型的基础上,对向列液晶nCB(4-n-alkyl-4'-cyano biphenyls,n=5-8)进行了等压等温NPT系综下的分子动力学(MD)模拟.对MD的轨迹分析得到了二阶和四阶序参数以及描述液晶分子翻转运动的取向时间相关函数(TCF),并通过一个近似的单指函数对TCF拟合得到了相关时间.在此基础上,计算了nCB(n=5-8)的旋转扩散系数(Rotat ional diffusion coefficient,RDC).利用基于统计力学模型的Nemtsov-Zakharov方法和Fialkowski方法,分别计算了它们的旋转黏度系数(rotational viscosity coefficient,RVC),进而分别讨论了RVC,RDC和相关时间的奇偶效应.与文献中的实验结果比较表明,该方法得到了合理的计算结果和一致的奇偶效应.     

Half-plane diffraction of Gaussian beams carrying two vortices of equal charges

This paper derives explicit expressions for the propagation of Gaussian beams carrying two vortices of equal charges m=±1 diffracted at a half-plane screen, which enables the study of the dynamic evolution of vortices in the diffraction field. It shows that there may be no vortices, a pair or several pairs of vortices of opposite charges m=+1, -1 in the diffraction field. Pair creation, annihilation and motion of vortices may appear upon propagation. The off-axis distance additionally affects the evolutionary behaviour. In the process the total topological charge is equal to zero, which is unequal to that of the vortex beam at the source plane. A comparison with the free-space propagation of two vortices of equal charges and a further extension are made.