Studying the length of trans conformational sequences in polyethylene using Raman spectroscopy: a computational study

The long standing question of how long a trans sequence in a polyethylene needs to be in order to contribute to the all-trans Raman bands at 1060 and 1130 cm⁻¹ is addressed. Various hexadecane, C₁₆H₃₄, conformers were studied using ab initio type calculations revealing vibrational frequencies and intensities. We found that only trans sequences longer than 10 trans bonds reveal Raman intensity primarily selectively at the same frequencies as the C-C stretching modes arising from crystalline polyethylene. Since it is statistically highly unlikely that such long trans sequences occur in the amorphous phase, intensity arising from all-trans sequences not belonging to crystalline structure may only be expected as a consequence of strong non-equilibrium conditions (e.g. shear), or the presence of tie-molecules.     

IR spectroscopic study of Pt/Kl zeolites using adsorption of CO as a molecular probe

FTIR spectra of CO adsorbed on Pt/KL catalysts show that the relative band intensities and the total dispersion markedly depend on the catalyst preparation method (ion exchange, incipient wetness impregnation or co-impregnation with KCl). The CO stretching frequency of the dominant band for linear CO is shifted to higher wavenumbers, parallel with the proton concentration in the reduced catalyst, which is derived independently from the intensity of the IR bands of the OH groups. The results are in accordance with the model that electron-deficient platinum particles are platinum-proton adducts.On leave from: N.D. Zelinsky Institute of Organic Chemistry, Academy of Sciences, Moscow, USSR.     

DX centers in AlxGa1-xAs bulk alloy,AlAs/GaAs ordered,and disordered superlattices

Properties of theDX centers in Al_0.5Ga_0.5As bulk alloy (b-AL), (AlAs)₂ (GaSa)₂ ordered superlattice (o-SL) and (AlAs) _m (GaAs) _n disordered superlattice (d-SL) (m = 1, 2, 3,n = 1, 2, 3) with the same macroscopic composition were measured and compared. By deconvolution of deep level transient spectroscopy (DLTS) spectrum due to theDX center, we have found a decrease in the number of separate peaks in DLTS spectrum in an intentionally atomic ordered arrangement. Visiting Scholar of the Japan Society for the Promotion of Science. On leave from Department of Electrical Engineering, San Jose State University, San Jose, California 95192-0084, USA.     

金属表面柴油机油沉积物的反射红外光谱法研究

利用镜反射红外光谱法研究了ＣＣ级柴油机油中添加剂对成漆板板面漆膜组成的影响：考察了成漆板漆膜组成与Ｃａｔ．１Ｈ２活塞环台漆膜组成的相关性。试验结果对柴油机油的研制和应用有一定指导作用。     

In Situ FTIR Study of the Formation of an Organosilane Layer at the Silica/Solution Interface

An FTIR experiment especially designed to study the growth of an organosilane layer at the interface between a solution and a flat silica surface is presented. High sensitivity is achieved by using the attenuated total reflection (ATR) technique in a liquid flow cell. The ATR crystal, either silicon or germanium, is covered with a very thin silica layer. Chemical reactions of a mono-and a di-hydrolyzable silane with the silica substrate have been investigated. The grafting of a submonolayer of the first reagent has been monitored by following the C-H and SiO-H vibrations. The density of grafted molecules has been estimated and information on the nature of the chemical bonding has been achieved. Evidence for the chain-polymerization of the dihydrolyzable silane at the substrate/solution interface has been inferred from the appearance of a Si-O-Si absorption band.     

An infrared spectroscopic study of the mechanism of chloromethane conversion to higher hydrocarbons on HZSM5 catalyst

Investigation of the reaction mechanism of chloromethane on ZSM5 is a new topic. In this work an in situ FTIR technique was employed to study the conversion processes of chloromethane, the active sites on HZSM5, and the desorption state of surface species. The catalytic conversion of chloromethane to higher hydrocarbons was also studied. It is demonstrated that chloromethane can be reversibly adsorbed on acidic sites of HZSM5 at room temperature. At 100°C chloromethane is irreversibly and dissociatively adsorbed on the strong acidic sites of HZSM5, on which surface methoxyl is formed as proved by infrared characteristic C-H stretchings of-CH₃ at 2960 and 2870 cm^–1. Alkoxyls are produced and adsorbed on the catalyst surface as characterized by the infrared absorption bands of -CH₂-groups at 1460 and 2930 cm^–1. At 100°C the adsorbed methoxyl and alkoxyls are the main surface species, and a small amount of aromatics might exist as detected by a characteristic absorption band at 1510 cm^–1. Between 100 and 200°C the adsorbed surface methoxyl and alkoxyls are converted to aromatics, and the occupied OH groups partially appear. At temperature higher than 300°C the adsorbed aromatics are thermally desorbed into the gas phase. Aromatics and alkanes are the main products in catalytic conversion. These results reveal that the formation of aromatics from methoxyl and alkoxyls is easier than the desorption of aromatics from HZSM5 catalyst. An alkoxyl mechanism is proposed for the conversion of chloromethane on HZSM5 based upon the experimental results and the three assumptions: (a) The primary C-C bond is formed from surface methoxyl groups via the methoxyl group polarization and C-H bond weakening, (b) The adsorbed alkoxyls are converted to aromatics via hydrogen transfer and bond rearrangement similar to the conventional carbenium ion mechanism for the aromatization of olefins and alkanes on HZSM5. The hydrogen atoms from the aromatization stimulate the desorption of alkoxyls to alkanes. (c) At temperature higher than 300°C surface reactions and desorption of adsorbed species take place simultaneously, determining the product distribution in the catalytic conversion.     

Direct Spectroscopic Determination of Europium(Ⅱ) Concentration During Europium(Ⅲ) Electro-Reduction in Hydrochloric Acid Medium

UV-Vis spectroscopy was used to directly determine the concentration of Eu(Ⅱ) during electroreduction of Eu(Ⅲ) in hydrochloric acid medium. Electroreduction was carried out in a flow type electrolyzer with glassy carbon cathode at the constant potential of -800 mV vs. Ag/AgCl. The effects of oxygen and concentration of hydrochloric acid on the system were investigated. For 0.01 mol·L-1 hydrochloric acid, calibration curves for Eu(Ⅱ) absorption bands at 248 and 320 nm were constructed. Molar absorption coefficients were estimated to be 2016 and 648 L·mol-1·cm-1, respectively. The absorbance strongly decreased with decrease in pH of the solution, whereas concentration of chloride had only a negligible effect.     

Progress in near-field photothermal infra-red microspectroscopy

Near‐field photothermal Fourier transform infra‐red microspectroscopy, which utilizes atomic force microscopy (AFM)‐type temperature sensors, is being developed with the aim of achieving a spatial resolution higher than the diffraction limit. Here we report on a new implementation of the technique. Sensitivity of the technique is assessed by recording infra‐red spectra from small quantities of analytes and thin films. A photothermomechanical approach, which utilizes conventional AFM probes as temperature sensors, is also discussed based on preliminary results. Early indication suggests that the photothermal approach is more sensitive than the thermomechanical one.     

Accurate measurement of capture cross sections in deep level transient spectroscopy: Application to EL2 in GaAs

A rigorous formulation of capacitance changes during trap filling processes is presented and used to accurately determine the electron capture cross section of EL2 in GaAs at a particular temperature, 377K, in this case. The value, σ_n (377K) = 2.7 × 10⁻¹⁶ cm², is compared with that predicted from the emission dependence.     

Argon I Lines Produced in a Hollow Cathode Source, 332 nm to 5865 nm

We report precision measurements by Fourier transform spectroscopy of the vacuum wavenumber, line width, and relative signal strength of 928 lines in the Ar I spectrum. Wavelength in air and classification of the transition are supplied for each line. A comparison of our results with other precision measurements illustrates the sensitivity of Ar I wavelengths to conditions in the light source.