The valence-shell electron momentum distributions for 1-butene are measured by electron momentum spectroscopy (EMS) employing non-coplanar symmetric geometry. The experimental electron momentum distributions are compared with the density functional theory (DFT) calculations using different-sized basis sets. Although the two conformers of 1-butene in the gas phase, namely the skew and syn, have very close ionization potentials, the electron momentum distributions, especially in the low momentum region, can show prominent differences for some of the valence orbitals. By comparing the experimental electron momentum profiles with the theoretical ones, the skew conformer is found to be more stable than the syn and their relative abundances at room temperature are estimated to be (69 +/- 6)% and (31 +/- 6)%, respectively. It demonstrates that EMS has the latent potential to study the relative stability of conformers.
The valence shell excitations of argon were investigated by an angle-resolved fast-electron energy-loss spectrometer at an incident electron energy of 2500 eV, and the transition multipolarities for the excitations of 3p → 3d, 4d, 5s, and 5p were elucidated with the help of the calculated intermediate coupling coefficients using the COWAN code. The generalized oscillator strengths for the excitations to 3p 5 ͑3d ,3dЈ͒, 3p 5 ͑5p ,5pЈ͒, and 3p 5 ͑5s ,4d͒ were measured, and the profiles of these generalized oscillator strength were analyzed. Furthermore, although the present experimental positions of the maxima for the electric-monopole and electricquadrupole excitations in 3p → 5p are in agreement with the theoretical calculations ͓Amusia et al., Phys. Rev. A 67, 022703 ͑2003͔͒, the generalized oscillator strength profiles show obvious differences. In addition, the experimental generalized oscillator strength ratios for the electric-octupole transitions in 3p → 3d are different from the theoretical prediction calculated by the COWAN code.
A gas sensor was developed by using the chemiluminescence (CL) emission from the oxidation of ethyl ether by oxygen in the air on the surface of borate glass. Theoretical calculation, together with experimental investigation, revealed the main CL reactions: ethyl ether is first oxidized to acetaldehyde and then to acetic acid, during which main luminous intermediates such as CH 3CO (*) are generated and emit light with a peak at 493 nm. At a reaction temperature of 245 degrees C, the overall maximal emission was found at around 460 nm, and the linear range of the CL intensity versus the concentration of ethyl ether was 0.12-51.7 microg mL (-1) ( R = 0.999, n = 7) with a limit of detection (3sigma) of 0.04 microg mL (-1). Interference from foreign substances including alcohol (methanol, ethanol and isopropanol), acetone, ethyl acetate, n-hexane, cyclohexane, dichloromethane, or ether ( n-butyl ether, tetrahydrofuran, propylene oxide, isopropyl ether and methyl tert-butyl ether) was not significant except a minimal signal from n-butyl ether (<2%). It is a simple, sensitive and selective gas sensor for the determination of trace ethyl ether.
A novel microplasma molecular emission spectrometer based on an atmospheric pressure dielectric barrier discharge (DBD) is described and further used as a promising multichannel GC detector for halohydrocarbons. The plasma is generated in a DBD device consisting of an outer electrode (1.2 mm in diameter) and an inner electrode (1.7 mm in diameter) within a small quartz tube (3.0 mm i.d. × 5.0 mm o.d. × 50 mm), wherein analyte molecules are excited by the microplasma to generate molecular emission. Therefore, the analytes are selectively and simultaneously detected with a portable charge-coupled device (CCD) via multichannel detection of their specific emission lines. The performance of this method was evaluated by separation and detection of a model mixture of chlorinated hydrocarbons (CHCl(3) and CCl(4)), brominated hydrocarbons (CH(2)Br(2) and CH(2)BrCH(2)Br), and iodinated hydrocarbons (CH(3)I and (CH(3))(2)CHI) undergoing GC with the new detector. The completely resolved identification of the tested compounds was achieved by taking advantages of both chromatographic and spectral resolution. Under the optimized conditions with the CCD spectrometer set at 258, 292, and 342 nm channels for determination of chlorinated hydrocarbons, brominated hydrocarbons, and iodinated hydrocarbons, respectively, this detector with direct injection provided detection limits of 0.07, 0.06, 0.3, 0.04, 0.05, and 0.02 μg mL(-1) for CCl(4), CHCl(3), CH(2)Cl(2), CH(3)I, CH(3)CH(2)I, and (CH(3))(2)CHI, respectively.
A simple and sensitive approach is proposed and evaluated for determination of ultratrace Zn and Cd in limited amounts of samples or tens of cells based on a novel single drop (5-20 μL) solution electrode glow discharge assisted-chemical vapor generation technique. Volatile species of Zn and Cd were immediately generated and separated from the liquid phase for transporting to atomic fluorescence or atomic mass spectrometric detectors for their determination only using hydrogen when the glow discharge was ignited between the surface of a liquid drop and the tip of a tungsten electrode. Limits of detection are better than 0.01 μg L(-1) (0.2 pg) for Cd and 0.1 μg L(-1) (2 pg) for Zn, respectively, and comparable or better than the previously reported results due to only a 20 μL sampling volume required, which makes the proposed technique convenient for the determination of Zn and Cd in limited amounts of samples or even only tens of cells. The proposed method not only retains the advantages of conventional chemical vapor generation but also provides several unique advantages, including better sensitivity, lower sample and power consumption, higher chemical vapor generation efficiencies and simpler setup, as well as greener analytical chemistry. The utility of this technique was demonstrated by the determination of ultratrace Cd and Zn in several single human hair samples, Certified Reference Materials GBW07601a (human hair powder) and paramecium cells.
The differential scattering cross sections and the generalized oscillator strengths of the 1 1 S→2 1 S and 1 1 S→2 1 P transitions of helium have been measured by angle-resolved electron-energy-loss spectroscopy with an incident electron energy of 1500 eV and within the range 2°-11.5°of scattering angles. The corrections for angular factors and density effects have also been made for the experimental results. The differential cross sections and generalized oscillator strength values are absolute and are the first to be measured at such a high impact energy. The experimental results are compared with other measurements and theoretical calculations in the literature.
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