Spin‐Selective Thermal Activation of Methane by Closed‐Shell [TaO3]+

Thermal reactions of the closed‐shell metal‐oxide cluster [TaO₃]⁺ with methane were investigated by using FTICR mass spectrometry complemented by high‐level quantum chemical calculations. While the generation of methanol and formaldehyde is somewhat expected, [TaO₃]⁺ remarkably also has the ability to abstract two hydrogen atoms from methane with the elimination of CH₂. Mechanistically, the generation of CH₂O and CH₃OH occurs on the singlet‐ground‐state surface, while for the liberation of ³CH₂, a two‐state reactivity scenario prevails.     

单块偏振片反射式向列相液晶显示器的理论设计与实验制造研究

反射式液晶显示器(RLCDs)具有亮度高、无视差等优点,并且结构简单,适合于现行的制造工艺和驱动方式.本文利用我们提出的参数空间法(偏振片角度、扭曲角及双折射率的函数)研究了适用于反射式液晶显示器,这种研究表明所有的反射式液晶显示模式都可以在这个参数空间里得以表述,如扭曲向列型的电控双折射模式(TN-ECB),混合场效应模式(HFE),混合向列型模式(MTN),以及自补偿向列型模式(SCTN).在此基础上我们提出几种新的反射模式,如反射向列型及反射超扭曲向列型(通过搜索参数空间得到),二者均适用于直视型和投影型显示方式.我们已制成反射向列型及反射超扭曲向列型样品,实验结果和理论设计符合一致.     

金刚石(111)氢化表面脱氢势垒的量子化学研究

采用MNDO(UHF)方法,计算金刚石(111)面的脱氢势垒。在与气相有机分子脱氢活化能实验值系统比较的基础上,在一组尺度不同的金刚石表面团簇模型上进行了计算,结果收敛于42±4kJ/mol.并与MNDO(RHF)和AM1(UHF、RHF)方法给出的相应结果进行了比较。     

Radical polymerization of ortho-(1,3-dioxolan-2-yl)phenyl ethyl fumarate involving intramolecular hydrogen abstraction and ring opening of cyclic acetal

The polymerization of o-(1,3-dioxolan-2-yl)phenyl ethyl fumarate (DOPEF) initiated with dimethyl 2,2′-azobisiso-butyrate (MAIB) was studied kinetically in benzene. The polymerization rate (R_p) at 60°C was given by R_p = k [MAIB]^0.76 [DOPEF]^0.71. The overall activation energy of polymerization was calculated to be 98.3 kJ/mol. The number-average molecular weight of resulting poly(DOPEF) was in the range of 1000–3100. ¹H- and ¹³C-NMR spectra of resulting polymers revealed that the radical polymerization of DOPEF proceeds in a complicated manner involving vinyl addition, intramolecular hydrogen abstraction, and further ring opening of the cyclic acetal at higher temperatures. From the copolymerization of DOPEF (M₁) and styrene (St) (M₂) at 60°C, the monomer reactivity ratios were obtained to be r₁ = 0.02 and r₂ = 0.20, the values of which are similar to those of the copolymerization of ethyl o-formylphenyl fumarate and St. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 563–572, 1998     

两种反射膜系的激光热力损伤特性

 在驻波场理论基础上,用表面和界面强吸收理论模型,计算出了激光辐照下两种不同反射膜系中温度场的“多峰”分布特性,分析了激光对薄膜的热力损伤特性、主要破坏模式和阈值条件。结果表明,光学薄膜对激光能量的吸收,主要由驻波场分布及膜层的消光系数决定;膜系表面的杂质吸附层和界面吸收层是膜系的主要能量沉积区,从而在这些界面形成温度场的“多峰”分布,界面因此成为最容易受激光损伤的部分。导致光学薄膜激光损伤的主要模式为膜层熔融和脱落两种。如果膜层中含有杂质,则容易诱导杂质处膜层剥落破坏。     

一种色度自适应投影标记点的选取方法

近年来,对物体的颜色显现力、光源光谱功率分布和自身表面反射光谱三者的定量关系方面的研究备受大家关注。在三维扫描测量领域,由于颜色特征具有反映物体材料和纹理等丰富信息的优势,提出了一种主要由彩色相机、投点光源和PC机组成的色度自适应投点仪结构,其中数字微镜(DMD)作为投点光源的核心元件用于调制R,G,B 三个LED光源的光谱功率分布。然而主动式标记点的颜色显现力因受未知反射光谱投影接受面的影响,其颜色特征往往难以识别和区分。为了提高投影标记点与不同反射光谱的投影接收面作为背景的分辨力,描述了一种色度自适应投影标记点的选取方法。在高维线性反射光谱建模的基础上,用光谱响应的方法对彩色投点仪设备特征化,以解决三通道彩色相机设备特征化精度低的问题。并通过样本训练为高维线性反射光谱的求解提供条件约束。继而,在CIE1931色度坐标空间下,选取与投影接收面背景色度坐标欧氏矩最大的色度坐标点。根据投点仪设备特征化结果,推导其LED最优设定值。最后,采用24孟塞尔色卡作为被投影对象,主动标记点与色块的色差作为其颜色显现力的评价参数,通过与激光二极管投点仪做对比性实验。实验结果表明对各不同色度的投点接受面,提出的色度自适应投影标记点的选取方法均有较好表现。     

叔丁氧基自由基引发氢迁移过程的理论研究

采用多种密度泛函理论方法(如CAM-B3LYP, M062x和wB97x方法), 并辅以极化连续介质模型对叔丁氧基自由基(^tBuO·)与一系列胺类、 烷烃、 醇类和醚类反应物之间氢迁移反应的反应机理进行研究. 计算结果表明, 这类氢迁移反应主要受熵的控制. 通过对液相平动熵和气相平动熵得到的活化自由能数据进行对比, 可以看出, 使用气相平动熵得出的活化自由能明显偏高于实验测量值, 而以液相平动熵计算的反应活化自由能垒与实际结果相近, 3种方法对胺类和烷烃类反应物体系得出的结果更可靠, 对醇类和醚类反应物体系自由能垒则略低.     

反射式流通池顺序注射光度检测系统的研制

提出一种反射式流通池用于过程分析光度检测系统 ,可以明显地抑制折光指数效应产生的干扰。以发光二极管为光源 ,采用多股光纤分别与流通池 ,光源 ,检测器耦合 ,实现对透射后反射回的光谱检测。以Cl- Hg(SCN) 2 Fe(Ⅲ )反应显色体系为模型对系统的实验参数进行了优化。讨论了试剂注入量、进样量、载流流速、试剂注入次序等参数对检测结果的影响。方法的线性范围为 0～ 10 0mg·L-1(相关系数r =0 998) ;分析精度 (RSD ,n =11)为 1 5 % ;检出限为 1 2mg·L-1;分析速度为 30个样·h-1;对自来水和海水的回收率分别为 95 %和 10 4 %。     

Theoretical Study on the Excited-state Intramolecular Hydrogen Abstraction Reactions of Butanal

The excited-state intramolecular hydrogen abstraction reactions of butanal have been investigated using the CAS-MP2/6-311＋G^＊//CASSCF/6-31G^＊ methods. Calculated results show that the hydrogen transfer induced fluorescence quenching of the n,π^＊-excited state of covalent butanal with three paths： （1） The first path corresponds to direct S0-react reconstitution, which involves the first S1 decay by partial hydrogen atom transfer. （2） The second stepwise mechanism can be viewed as a full hydrogen atom transfer followed by a partial hydrogen atom back transfer, electron transfer （near S1/S0 or S0-TS） and finally a proton transfer to S0-react. （3） On the triplet surface, the surface crossing to the singlet state would be clearly much efficient at the T1/S0 region due to the large SOC value of 8.3 cm^-1. The S0-react decay route from T1/S0 was studied with an intrinsic reaction coordinate （IRC） calculation at the CASSCF level, resulting in the S0-React minimum.     

Theoretical investigation of the kinetics for the hydrogen abstraction reaction of 1,1,1,2-tetrafluoroethane (HFC-134a) by chlorine radical

The hydrogen abstraction reaction of 1,1,1,2-tetrafluoroethane (HFC-134a) by chlorine radical is investigated by theoretical calculations. Equilibrium geometries and harmonic vibrational frequencies of the reactants, transition state, and products are calculated using high-level ab initio methods. Rate constants of forward and backward reactions for the temperatures from 200 to 1000 K are calculated using classical transition state theory with Eckart tunneling correction, fitted in the expressions k_f (T) = 1.19 × 10⁻²³T^3.93exp (−1110/T), and k_b (T) = 8.86 × 10⁻²⁴T^3.32exp (−959/T) cm³ molecule⁻¹ s⁻¹ for forward and backward reactions, respectively, and are in reasonable agreement with the available experimental values.