A Semiconductor Laser of the Visible Range as an Exciting Source of Raman Scattering

A possibility of application of semiconductor lasers of the visible range as exciting sources for Raman spectroscopy is studied. An experimental set-up for measuring Raman spectra of polycrystalline dielectrics and broad-gap semiconductors excited by a semiconductor laser with a wavelength of 640 nm was created. The conditions under which the spectral width of the lasing line of a semiconductor laser was within 10^-3 cm^-1 in the continuous mode with a power of 10 mW are realized. The characteristics of various types of exciting sources used in Raman spectroscopy are compared. The results of studies of the characteristic Raman spectra excited with a semiconductor laser in polycrystalline sulfur are presented.     

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

Design and synthesis of Ru(II-bipyridyl-containing conjugated polymers

A series of novel π-conjugated polymers containing ruthenium bipyridine complexes was synthesized by a cross-coupling reaction and characterized. These polymers exhibit absorption maxima around 330–350 nm (π-π*) and 460–500 nm metal-to-ligand charge transfer (MLCT), respectively. They are soluble in common organic solvents, and all polymers can be converted into transparent films. We investigated the influence of different donating and acceptor diethynylarenes of the ultraviolet-visible spectra. The oxidation potential, which was measured by cyclic- and square-wave voltametry, showed a typical Ru^2+/3+ exhibited at 1.25 V versus the saturated calomel electrode. The polymers were further characterized with photoluminescence measurements. When excited at 442 nm ( 11a ), the polymer exhibited an emission peak at 690 nm. This peak was attributed to the MLCT states. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 722–732, 2004     

Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Segmental and secondary dynamics in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) blends

Broadband dielectric spectroscopy was used to study the segmental (α) and secondary (β) relaxations in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) (PVPh/PMMA) blends with PVPh concentrations of 20–80% and at temperatures from ?30 to approximately glass‐transition temperature (T_g) + 80 °C. Miscible blends were obtained by solution casting from methyl ethyl ketone solution, as confirmed by single differential scanning calorimetry T_g and single segmental relaxation process for each blend. The β relaxation of PMMA maintains similar characteristics in blends with PVPh, compared with neat PMMA. Its relaxation time and activation energy are nearly the same in all blends. Furthermore, the dielectric relaxation strength of PMMA β process in the blends is proportional to the concentration of PMMA, suggesting that blending and intermolecular hydrogen bonding do not modify the local intramolecular motion. The α process, however, represents the segmental motions of both components and becomes slower with increasing PVPh concentration because of the higher T_g. This leads to well‐defined α and β relaxations in the blends above the corresponding T_g, which cannot be reliably resolved in neat PMMA without ambiguous curve deconvolution. The PMMA β process still follows an Arrhenius temperature dependence above T_g, but with an activation energy larger than that observed below T_g because of increased relaxation amplitude. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3405–3415, 2004     

二氟甲烷分子3a1和2b2轨道的电子动量谱

借助电子动量谱学结合量子化学理论和其他方法可以给出轨道电子在整个空间的分布信息,由此给出电子运动的完备描述[1,2 ] .清华大学电子动量谱学实验室近几年已成功地对甲烷[3] 、异丁烷[4 ] 、环戊烷[5] 、二乙酰等[6 ] 分子的轨道电子动量分布进行了测量.我们利用第二代电子动量谱仪首次对CH2 F2 分子3a1和2b2 轨道的电子动量谱进行测量,并与理论计算结果作了比较.同时还计算了坐标空间和动量空间中电子在x - y平面的密度分布.电子动量谱学最基本的过程是(e ,2e)反应,即电子与靶粒子碰撞而发生的电离过程.而对于(e ,2e)反应,含有大量信…     

聚乙烯基咔唑与Alq3混合薄膜的发光性能与能量传递过程

研究了Alq3与聚乙烯基咔唑(PVK)按不同比例的混合体系制备的薄膜的发光特性.通过对混合薄膜的吸收光谱、激发光谱和发射光谱的分析，研究了PVK与Alq3之间的 能量传递规律.当Alq3与PVK的质量比为1∶7时，能量传递效率最高.用一个由单链模 型扩展到包括杂质的哈密顿量对实验进行模拟，发现该模型能够较好地解释有关的实验结果. 关键词： 吸收光谱 激发光谱 发射光谱 能量传递     

Yb3+掺杂铝氟磷酸盐玻璃的光谱和激光性能

研究了Yb3 掺杂铝氟磷酸盐 (AFP)玻璃的吸收光谱、荧光光谱 ,测量了Yb3 离子的荧光有效线宽 (Δλeff>5 5nm)以及2 F5 2 能级的荧光寿命 (τmax=2ms)及随掺杂浓度的变化 .应用倒易法计算了Yb3 的发射截面 ,其发射截面可达 0 6 6 82 3pm2 ,且激光增益系数τfσemi达 1 2 89ms.pm2 .评估了Yb3 在AFP玻璃中的激光性能 ,发现其具有较理想的激发态最小粒子数 (0 15 )、饱和抽运强度 (8 3kW cm2 )和最小抽运强度 (1 2 4 5kW cm2 )值及良好的热稳定性 .研究结果表明掺Yb3 氟磷酸盐玻璃是实现高功率超短可调谐激光器的理想增益介质 .     

含氮类金刚石薄膜的紫外辐照研究

 用射频等离子体方法在玻璃基底上制备的类金刚石（DLC）薄膜，采用离子注入法掺氮，并对掺氮DLC薄膜紫外（UV）辐照前后的性能变化进行了研究。研究结果表明：随氮离子注入剂量及UV辐照时间的增加，位于2 930cm^-1附近的SP ³C-H吸收峰明显变小，而位于1 580cm^-1附近的SP2C-H吸收峰则明显增强，薄膜的电阻率明显呈下降趋势；随UV辐照时间的增加，位于1 078cm^-1附近的Si-O-Si键数量及位于786cm^-1附近的Si-C键数量明显增加。即氮离子注入和UV辐照明显改变了DLC薄膜的结构与特性。