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11.
P. Macko D. Romanini O.V. Naumenko A. Jenouvrier A. Campargue 《Journal of Molecular Spectroscopy》2004,227(1):90-108
The absorption spectrum of natural water vapour around 1.5 μm has been recorded with a typical sensitivity of 5 × 10−10 cm−1 by using a CW-cavity ring down spectroscopy set up based on fibred DFB lasers. A series of 31 DFB lasers has allowed a full coverage of the 6130.8-6748.5 cm−1 (1.63-1.48 μm) region corresponding to the H transparency band of the atmosphere. The line parameters (wavenumber and intensity) of a total of 5190 lines, including 4247 lines of water vapor, were derived by a one by one fit of the lines to a Voigt profile. Different isotopologues of water (H216O, H218O, H217O, and HD16O) present in natural abundance in the sample contribute to the spectrum. For the main isotopologue, H216O, 2130 lines were measured with line intensities as weak as 10−29 cm/molecule while only 926 lines (including a proportion of 30% inaccurate calculated lines) with a minimum intensity of 3 × 10−27 cm/molecule are provided by the HITRAN and GEISA databases. Our comparison in the whole 5750-7965 cm−1 region, has also evidenced that an error in the process of conversion of the intensity units from cm−2/atm to cm−1/(molecule × cm−2) at 296 K, has led to H216O line intensities values listed in the HITRAN-2000 database, systematically 8 % below the original FTS values. The rovibrational assignment was performed on the basis of the ab initio calculations by Schwenke and Partridge with a subsequent refinement and validation using the Ritz combination principle together with all previously measured water transitions relevant to this study. This procedure allowed determining 172, 139, 71, and 115 new energy levels for the H216O, H218O, H217O, and HD16O isotopologues, respectively. The results are compared with the available databases and discussed in regard of previous investigations by Fourier transform spectroscopy. The spectrum analysis has showed that most of the transitions which cannot be assigned to water are very weak and are due to impurities such as carbon dioxide and ammonia, leaving only about 3% of the observed transitions unassigned. The interest of a detailed knowledge of water absorption for trace detectors developed in the 1.5 μm range is underlined: for instance HDO contributes significantly to the considered spectrum while no HDO line parameters are provided by the HITRAN database. 相似文献
12.
软x射线近贴显微技术 总被引:1,自引:0,他引:1
软x射线近贴显微技术不但可使活的生物样品成象,分辨率高于光学显微镜,而且人为的样品准备程序在该技术中都可避免。本文描述了用高功率激光打靶产生的等离子体作为软x射线源而进行的近贴显微研究,并得到了分辨率好于1μm的结果。 相似文献
13.
14.
有机化合物在光窗上的结焦严重地影响激光引发化学反应及光学原位实时探测。本文报道在1,2-二氯丙烷反应系统中,光窗结焦现象同时存在于激光引发反应及热反应过程中,对光窗在300℃条件 下的结焦机理研究表明,少量氧气在光窗结焦过程中起关键作用。结焦前驱体的红外光谱研究表明,前驱体的可能结构为1-丙炔-1,3-二醇的缩聚体。该化合物极易通过缩聚反应形成更大的分子,最终导致光 窗结焦。对系统及反应物进行彻底除氧,光窗结焦现象大为改善。 相似文献
15.
《Electroanalysis》2004,16(12):994-1001
The interfacial behavior of electrodes fabricated from carbon film resistors of 2 and 20 Ω in supporting electrolyte solutions of varying pH used in electroanalytical experiments has been characterized by electrochemical impedance spectroscopy with complementary cyclic voltammetric experiments. Equivalent circuits are proposed to fit the experimental data and the influence of electrode pretreatment has also been investigated. 相似文献
16.
S. Jayaraman R. Srinivasan J. E. McGrath 《Journal of polymer science. Part A, Polymer chemistry》1995,33(10):1551-1563
The synthesis of 3-phenylethynylphenol, and its applicability as a high temperature cross-linking endcap for high Tg polyarylene ethers is described. It was synthesized in high yields and purity using the palladium catalyzed coupling reaction between the protected 3-bromo or iodo phenol and phenylacetylene. The yield of the reaction was found to be highly dependent on the structure of the halide used, the reaction temperature, and the concentration of phenylacetylene. The use of the protected phenol in the palladium catalyzed reaction was also extended to the high yield synthesis of 3-ethynylphenol and protected 4-ethynylphenols. The complete synthesis of 3-phenylethynylphenol, 3-ethynylphenol, and protected 4-ethynylphenol in high yields has been demonstrated and is discussed herein. Three new phenylethynyl functionalized arylene ether matrix resins have been synthesized in high yields and purity by reacting 3-phenylethynylphenol with 4,4′-dichlorodiphenyl sulfone, 4,4′-difluorobenzophenone, and bis(4-fluorophenyl)phenyl phosphine oxide, via nucleophilic poly(arylene ether) synthesis conditions. These low molecular weight materials undergo thermally induced chain extension/branching to yield an insoluble three-dimensional network at reaction temperatures of around 380°C. The low molecular weight arylene ethers endcapped with the phenylethynyl group demonstrate excellent flow characteristics and a wide processing window of about 250°C. Crosslinking of the 4,4′-bis(3-phenylethynyl phenoxy)diphenyl sulfone system for 30 min at 350°C in air afforded a Tg value of 265°C by differential scanning calorimetry measurements. Trace metal analysis for palladium and copper showed absence of these metals that would otherwise detract from the excellent thermal stability. The synthesis and characterization of these phenylethynyl endcapped arylene ether matrix resins is discussed. © 1995 John Wiley & Sons, Inc. 相似文献
17.
Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions. 相似文献
18.
Isothermal pressure (p)-mass fraction (w) phase diagrams were measured for CO2 + tetradecanoic acid at six temperatures from 328.2 K to 373.2 K and for CO2 + docosane at four temperatures from 343.2 K to 393.2 K as well as isobaric temperature (T)-mass fraction (w) phase diagrams for both systems at 34.5 MPa. In addition the isothermal and isobaric Gibbs phase prisms at 373.2 K and 34.5 MPa respectively were determined for the ternary system CO2 + tetradecanoic acid + docosane, and and isobaric miscibility window was found between 333 K and 385 K at 34.5 MPa. 相似文献
19.
Time shift correction in second-order liquid chromatographic data with iterative target transformation factor analysis 总被引:4,自引:0,他引:4
Enric Comas R. Ana Gimeno Joan Ferr Rosa M. Marc Francesc Borrull F. Xavier Rius 《Analytica chimica acta》2002,470(2):607-173
When the generalized rank annihilation method (GRAM) is applied to liquid chromatographic data with diode-array detection, an important problem is the time shift of the peak of the analyte in the test sample. This problem leads to erroneous predictions. This time shift can be corrected if a time window is selected so that the chromatographic profile of the analyte in the test sample is trilinear with the peak of the analyte in the calibration sample. In this paper we present a new method to determine when this condition is met. This method is based on the curve resolution with iterative target transformation factor analysis (ITTFA). The calibration and test matrices are independently decomposed into profiles and spectra, and aligned before GRAM is applied. Here we study two situations: first, when the calibration matrix has one analyte and second, when it has two analytes. When the calibration matrix has two analytes, we selectively determine the time window for the analyte to be quantified. There were considerably fewer prediction errors after correction. 相似文献
20.