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.     

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。     

Structural and vibrational properties of dilute GaNxAs1−x(P1−x)

We report a comprehensive analyzes of the Fourier transform infrared (FTIR) absorption and Raman scattering data on the structural and vibrational properties of dilute ternary GaAs_1−xN_x,[GaP_1−xN_x] (x<0.03) alloys grown on GaAs [GaP] by metal organic chemical vapor deposition (MOCVD) and solid source molecular beam epitaxy (MBE). By using realistic total energy and lattice dynamical calculations, the origin of experimentally observed N-induced vibrational features are characterized. Useful information is obtained about the structural stability, vibrational frequencies, lattice relaxations and compositional disorder in GaNAs (GaNP) alloys. At lower composition (x<0.015) most of the N atoms occupy the As [P] sublattice {N_As[N_P]}—they prefer moving out of their substitutional sites to more energetically favorable locations at higher x. Our results for the N-isotopic shifts of local mode frequencies compare favorably well with the existing FTIR data.     

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     

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.     

Liquid-phase chlorination ofC-chlorovinylsilanes

Liquid-phase chlorination of a number of chloro(chlorovinyl)methylsilanes was investigated. A number of novelC-chlorosilanes were characterized by IR and¹H NMR spectra. Some regularities of these reactions were determined; correlations between the structure of chloro(chlorovinyl)methylsilanes and their reactivities were identified.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2256–2260, November, 1995.     

He-N2 radiofrequency discharge: Influence of N2 on discharge and afterglow

A diagnostic study q (energy transfer processes in a He-N₂ flowing discharge and afterglow has been performed in a radiofrequency-produced plasma cooled in a liquid nitrogen hath. Optical emission spectroscopy in the visible and infrared spectral range as well as Langrnuir probe diagnostics were used. The vibrational kinetics of CO injected in such an afterglow has been examined. It shows a slow cooling of the electrons in the afterglow regime. The electron kinetics responsible joy CO vibrahonal excitation is turned off when N₂ is added to the He discharge, while that for vibrationally excited N₂ molecules is turned on. The results are discussed on the basis of previous theorerical calculations and experiments on the He-N₂ system.