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3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3). 相似文献
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Magnesium atoms generated by laser ablation were reacted with methyl halides and methane diluted in argon. Among the reaction products were the metal carbene species, MgCH2, and carbenoid radicals, XMgCH2 (where X = H, F, Cl, and Br). This investigation reports matrix infrared spectra for Mg carbene and carbenoid species in a cold matrix, and electronic structure calculations for these and related beryllium species. An unusual bonding interaction for the MCH2 species is described in which the bonding in the alpha and beta manifolds is qualitatively different. Vibrational frequencies and analysis of the results of density functional calculations provide information about the nature of the bonding in these species and allow for a comparison to the well-known transition metal Fischer- and Schrock-type carbene complexes. The special difficulties of computational modeling of vibrations in highly polar molecules are discussed. 相似文献
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Hydrogen adsorption on Pt(6)H(n) clusters leads to striking changes in the Pt L(2,3) x-ray absorption spectra. These effects are interpreted using a self-consistent real space Green's function approach. Calculations show that they are due largely to changes in the atomic background contribution to x-ray absorption (i.e., atomic x-ray absorption fine structure) and to reduced Pt-Pt scattering at the edge, while Pt-H multiple scattering is relatively weak. The origin of both effects is traced to the change in the local Pt potential due to Pt-H bonding. 相似文献
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The emission spectra of four mercury vapor lamps are used to obtain wavelength calibration curves for the double-grating emission monochromator of a spectrofluorimeter. The use of second- and third-order diffraction lines and emission lines from the argon carrier gas provides a rich spectrum, which extends well into the near-infrared spectral region and produces an improved calibration curve. More than 60 emission lines are listed between 250 and 900 nm, which is sufficient to produce an extremely accurate monochromator calibration. Additional second- and third-order lines can be used to even longer wavelengths (>1200 nm). The effectiveness of three scattering surfaces is compared. 相似文献
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Nathan H. Mack William D. Bare Wenying Xu J. N. Demas B. A. DeGraff 《Journal of fluorescence》2001,11(2):113-118
An apparatus is described for the automated collection of luminescence emission decay curves over a wide range of analyte concentrations. The decay curves allow for determination of the excited-state lifetime or calculated steady-state intensity of a luminophore as a function of the analyte concentration. The data presented here demonstrate the use of the apparatus for pH titrations. 相似文献
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M.H. Majles Ara SR. Hosseini M.H. Rezvani M. Abolhassani 《Journal of Physics and Chemistry of Solids》2011,72(11):1367-1372
In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO3 photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering. 相似文献
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Michael X. Yang Phillip W. Kash Dong-Hong Sun George W. Flynn Brian E. Bent Michael T. Holbrook Simon R. Bare Daniel A. Fischer John L. Gland 《Surface science》1997,380(2-3):151-164
The bonding and reactions of chloroethylenes (vinyl chloride, trans- and cis-dichloroethylene, trichloroethylene) on a Cu(100) surface have been investigated by temperature-programmed desorption and reaction, near-edge X-ray absorption fine structure (NEXAFS) studies and measurements of changes of the surface work function. The monolayer molecules adsorb molecularly intact at 95 K via π coordination. The molecules orient with their molecular planes parallel to the surface with little increase (<0.02 Å) in the C---C bond distance compared with the gas phase values. The degree of thermal dissociation increases with the extent of halogenation, and no chlorine is present in the hydrocarbon reaction products liberated from the surface. Both cis- and trans-1.2-chloroethylene produce acetylene and a small amount of benzene, while dissociation of trichloroethylene generates acetylene and deposits a carbon residue on the surface. Vinyl chloride desorbs from Cu(100) without reaction. 相似文献
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S.R. Bare K. Griffiths P. Hofmann D.A. King G.L. Nyberg N.V. Richardson 《Surface science》1982,120(2):367-375
Using both synchrotron and HeII radiation the electronic and geometric structure of Pt{110}-(2×1)p1g1 CO was examined. The shape resonance for the 4σ orbital of CO is found to be peaked at 38 eV, while that for the 5σ orbital is peaked at 28 eV. No shape resonance is observed from the 1π orbital. The ordering is reversed from that of gas phase CO. Further evidence, from the polar intensity variation of the non-bonding 4σ orbital, is presented for the tilted CO structure proposed previously. 相似文献