Algebraic methods in quantum mechanics: from molecules to polymers

We present a brief review of algebraic techniques developed and applied in molecular spectroscopy in the last five years. We also outline perspectives for new applications of the Lie algebraic method in the first decade of the new century. Received 21 November 2001     

Global fit analysis including the ν9 + ν4 − ν4 hot band of ethane: Evidence of an interaction with the ν12 fundamental

The ν₉ fundamental band of ethane occurs in the 12 μm region. It is the strongest band of ethane in a terrestrial window and is commonly used for the identification of ethane in the Jovian planets. The ν₉ + ν₄ − ν₄ band occurs in the same region; neither can be analysed as an isolated band, since both are embedded in the torsional bath of the ground vibrational state. We report here two global fit models including data from both of these bands as well as the ν₃ fundamental and the ν₄, 2ν₄ − ν₄, and 3ν₄ torsional transitions. The first is restricted to −5 ? KΔK ? 15 in the hot band and gives an excellent fit to the included data. Three resonant interactions are identified in this fit—a Coriolis interaction with two resonant cases between the ν₉ torsional stack and that of the ground vibrational state (gs) and a resonant Fermi interaction between the ν₃ fundamental and the gs. Hot band lines with KΔK < −5 are influenced by a fourth perturbation, with a crossing at −11 < KΔK < −10, which has been attributed to an interaction with the ν₁₂ fundamental. A second fit, demonstrating a promising treatment of this interaction, is also presented.     

大口径宽视场双波段扫描红外相机光学设计

通过分析计算,设计了一种大口径宽视场折射式红外相机光学系统。该系统设计用于超长线阵扫描红外相机的地面演示成像,它能同时对短波2μm—3μm、中波3μm—4.5μm双波段成像,且同时具有24°的大视场和150mm的宽口径,成像质量接近衍射极限。该系统在航天遥感领域应用广泛。     

Chlorination of aromatic substrates catalyzed by the phthalocyanine complexes

The chlorination of benzene, toluene, and o-xylene with molecular chlorine in the presence of the phthalocyanine complexes of different structures was studied. The transformations of the catalysts during the reaction were investigated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1644–1647, August, 2008.     

含氟碳菁染料聚集行为的研究

本文对五种不同结构的含氟碳菁染料的甲醇溶液及吸附在碘溴化银T 颗粒表面的聚集行为进行了研究 ,测定了照相性能 ,计算了增感倍率。Dye1 ,Dye2 ,Dye3在甲醇溶液中测得的单分子态吸收曲线 ,当取代基从C2 H5→CH3→无取代基时 ,最大吸收峰对应的波长向短波方向移动 ;乙基取代基的增感染料 (Dye1 )吸附在碘溴化银表面形成的J 聚集态峰值较高 ,对应的增感倍率也高。没有取代基的增感染料 (Dye3)不形成J 聚集 ,增感倍率低 ,有减感作用。Dye4与Dye5相比 ,Dye4具有尖而窄的J 聚集反射光谱 ,增感倍率高。结果表明 :不同结构的增感染料吸附在卤化银颗粒上形成的J 聚集态不同 ,吸收谱带窄的J 聚集态增感染料具有较高的增感倍率。     

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     

Electromagnetic energy flow near nanoparticles—I: single spheres

The electromagnetic (EM) energy flow near single spheres is investigated by applying Mie theory. From the patterns of the energy flow, the absorption and the scattering of light can be understood in the microscopic point of view. In the absorption profiles of metallic particles, most absorbed energy is consumed on the surface of the particles, which indicates that the resonance of surface plasmon is different from that of the bulk plasmon. Two mechanisms to enhanced local EM field are also distinguished. One is the surface plasmon resonance, and another one is the intensified energy flow.     

Chemical synthesis and electric properties of the conducting copolymer of aniline and o‐aminophenol

A copolymer, poly(aniline‐co‐o‐aminophenol), was prepared chemically by using ammonium peroxydisulfate as an oxidant. The monomer concentration ratio of o‐aminophenol to aniline strongly influences the copolymerization rate and properties of the copolymer. The optimum composition of a mixture for the chemical copolymerization consisted of 0.3 M aniline, 0.021 M o‐aminophenol, 0.42 M ammonium peroxydisulfate, and 2 M H₂SO₄. The result of cyclic voltammograms in a potential region of ?0.20 to 0.80 V (vs.SCE) indicates that the electrochemical activity of the copolymer prepared under the optimum condition is similar to that of polyaniline in more acid solutions. However, the copolymer still holds the good electrochemical activity until pH 11.0. Therefore, the pH dependence of the electrochemical property of the copolymer is improved, compared with poly(aniline‐co‐o‐aminophenol) prepared electrochemically, and is much better than that of polyaniline. The spectra of IR and ¹H NMR confirm that o‐aminophenol units are included in the copolymer chain, which play a key role in extending the usable pH region of the copolymer. The visible spectra of the copolymers show that a high concentration ratio of o‐aminophenol to aniline in a mixture inhibits the chain growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5573–5582, 2007     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.     

Possible spectroscopic manifestation of the angular group induced bond alteration (AGIBA) effect in toluene

The most obvious consequence of the concept of aromaticity is the common confidence that in aromatic compounds, bond lengths do not alternate and are between typical to the single and double ones. However, in 1994, performing crystal structure investigations of substituted pyridines and their salts, Krygowski and co‐workers have discovered a very surprising angular group induced bond alteration (AGIBA) effect: It appears that some angular substituents, like methoxy or nitrozo groups, can induce bond alternation in aromatic rings. Crystal studies do not allow one to operate with liquids that are more common in organic chemistry. This paper presents the first possible evidence of spectroscopic manifestations of the AGIBA effect. Raman spectra of the liquid toluene are analyzed. It is found that instead of being single, the line corresponding to the ring breathing vibrations is clearly split by 1.0–1.4 cm^?1, thus indicating the presence of two (cis‐ and trans‐) AGIBA isomers. The energy difference between these isomers estimated in temperature dependent Raman studies is found equal to 6.68 kJ mol^?1. The low‐wavenumber line therefore corresponds to the cis‐AGIBA isomer and the high‐wavenumber line to the trans‐AGIBA isomer stabilized by the AGIBA effect. Copyright © 2007 John Wiley & Sons, Ltd.