Time-resolved single-crystal diffraction performed with synchrotron radiation shows that the 53(1) micros phosphorescent state, generated in the crystalline phase of trimeric {[3,5-(CF3)(2)Pyrazolate]Cu}(3) molecules by exposure to 355 nm of light at 17 K, is due to the formation of an excimer rather than the shortening of the intramolecular Cu...Cu distances within the trimeric units, or the formation of a continuous chain of interacting molecules. One of the intermolecular Cu...Cu distances contracts by 0.56 Angstroms from 4.018(1) to 3.46(1) Angstroms;, whereas the interplanar spacing of the trimers is reduced by 0.65 Angstroms; from 3.952(1) to 3.33(1) Angstroms. Density-functional theory calculations support the formation of a Cu...Cu bond through the intermetallic transfer of a Cu 3d electron to a molecular orbital with a large 4p contribution on the reacting Cu atoms. 相似文献
Formation of the plasma potential in a plasma that contains energetic electrons and is bounded by a floating collector that
emits electrons is studied theoretically. The problem is treated by a static. kinetic plasma-sheath model of Schwager and
Birdsall [Phys. Fluids B2 (1990) 1057], which we have extended in order to include additional energetic electron population. The distribution of these
electrons is assumed to be a high-temperature Maxwellian. They are called hot electrons. In the paper we study effects of
the density and temperature of the hot electrons on the formation of the plasma potential. The model shows that for certain
densities and temperatures of the hot electron population plasmas with two different plasma potentials can coexist in the
system. These two plasmas are separated spatially by a double layer. For the case when there is no emission of electrons from
the collector, results of the model are compared with computer simulation and very good agreement between the model and the
simulation is found. The simulation also confirms existence of two plasmas with two different potentials separated by a double
layer. 相似文献
The reduction of [Co(III)(tmsalen)py(2)](+)ClO(4)(-), where tmsalen = 4,4',7,7'-tetramethylsalen, with NaBH(4)/PdCl(2) in alkaline methanolic solution, followed by the oxidative addition of CH(2)ClI, leads to the expected trans organometallic dimeric species 1, [CH(2)ClCo(tmsalen)](2), provided that the product is recovered from the reaction mixture immediately after the completion of the reaction. If 1 is left for longer time in contact with the reaction mixture, the intramolecular reaction of the axial chloromethyl group with the equatorial chelate leads to the formation of the monocationic complex 2, containing a seven-membered ring. In this complex the novel tetradentate ligand coordinates Co in a cis fashion, the other two positions being occupied by one py and one water molecule. The resulting complex is chiral, even if the reaction product is a racemic compound. The unidentate ligands of 2 have been exchanged quantitatively for N-MeIm, and the resulting complex 3 still maintains the beta cis geometry. Therefore, 2 may be considered the precursor of a new class of organocobalt derivatives with a folded tetradentate ligand and two adjacent exchangeable sites. On the basis of the geometry of the tetradentate Schiff bases in complexes, where they adopt a planar geometry, it was suggested that there is a significant electron density delocalization involving the metal center over the two chemically equivalent moieties of Co(chel). Comparison of the geometry of the planar salicylaldiminate (sal) moiety with that of the cyclized methoxy-iminate one (imi) in 2 and 3 strongly supports that the delocalization, still present in sal, is essentially either lost or strongly reduced in imi. 相似文献
Conventional electrothermal atomic absorption spectrometric (ETAAS) equipment was extensively modified to enable automated in situ electrodeposition. The original autosampler injection Teflon capillary was replaced by a composite Pt/Teflon capillary which served as an anode in the electrodeposition circuit. Incorporation of a peristaltic pump and of a three-way solenoid under computer control into the sample dispenser circuit provided all necessary steps for automated electrodeposition-ETAAS determination. The automated sequence controlled addition of Pd modifier and of the analyte, electrolysis, withdrawal of spent electrolyte, rinsing, drying and atomization. Performance of the system was evaluated by analyzing Pb in 3% m/v NaCl. Optimization using factorial design yielded 3sigma detection limit of 20 pg Pb and reproducibility of 1.0-1.4% (for constant current electrodeposition), these values being superior to the results of conventional ETAAS of Pb in 0.5% m/v NaCl. Sensitivity of Pb determination is not affected by NaCl, NaOH, NaNO3 and NH4H2PO4, up to 4.6% m/v, demonstrating efficient matrix removal in the electrodeposition step. 相似文献
Fast direct solvers for the Poisson equation with homogeneous Dirichlet and Neumann boundary conditions on special triangles and tetrahedra are constructed. The domain given is extended by symmetrization or skew symmetrization onto a rectangle or a rectangular parallelepiped and a fast direct solver is used there. All extendable domains are found. Eigenproblems are also considered. 相似文献
A theorem of M. F. Driscoll says that, under certain restrictions, the probability that a given Gaussian process has its sample paths almost surely in a given reproducing kernel Hilbert space (RKHS) is either or . Driscoll also found a necessary and sufficient condition for that probability to be .
Doing away with Driscoll's restrictions, R. Fortet generalized his condition and named it nuclear dominance. He stated a theorem claiming nuclear dominance to be necessary and sufficient for the existence of a process (not necessarily Gaussian) having its sample paths in a given RKHS. This theorem - specifically the necessity of the condition - turns out to be incorrect, as we will show via counterexamples. On the other hand, a weaker sufficient condition is available.
Using Fortet's tools along with some new ones, we correct Fortet's theorem and then find the generalization of Driscoll's result. The key idea is that of a random element in a RKHS whose values are sample paths of a stochastic process. As in Fortet's work, we make almost no assumptions about the reproducing kernels we use, and we demonstrate the extent to which one may dispense with the Gaussian assumption.
The iron silicides samples were prepared by annealing of iron films evaporated onto silicon wafers and capped with amorphous silicon thin overlayers. Semiconducting FeSi2 phase is formed by annealing at the temperatures from 550°C to 850°C. The optical properties of the FeSi2 layers have been deduced from reflectance and transmittance measurements carried out in the temperature range of (77–380) K. The spectral dependence of the absorption coefficient favours direct allowed transitions with forbidden energy gap of 0.87eV at the room temperature. The application of a simple three-parameter semiempirical formula to the temperature dependence of the direct energy gaps leads to the following best fit parameters: the band gap at zero temperature Eg (0) = (0.895 ± 0.004)eV, the dimensionless coupling parameter S = 2.0 ± 0.3, and the average phonon energy <hw> = (46 ± 8)meV. By examining all the reported triplets of parameters for -FeSi2 fabricated by different techniques and thermal processes, an obvious discrepancy can be found for the lattice coupling parameter and average phonon energy, although the bandgaps at 0 K are very similar. Unlike the theoretical prediction and the earlier reported result, our results do not show any evidence of a particularly strong electron-phonon interaction, which would give the lower carrier mobilities. -FeSi2 seems to be an intriguing material where states with energies near the band edges permit ambiguous interpretation of the character of transitions. From optical model for the thin film-substrate system we found the index of refraction to be (5–5.9) in the photon energy interval from 0.65 to 1.15eV. There is also indication of an additional higher-energy absorption edge at l.05eV. 相似文献
A preparative procedure for the synthesis of an important chiral synthon of side-chain protected tyrosine was developed and optimised for the minimisation of nickel salts waste. While preparing a similar side-chain protected tryptophan synthon, an unexpected low stability was found of the Boc-protective group of the tryptophan aromatic nitrogen during purification on silica gel. X-ray crystal structure determination, tandem mass spectrometry (MS/MS) and NMR were applied for the elucidation of the structures of the prepared complexes and by-products. Stereochemistry of products of α-methylation of the complexes was assessed using a model tyrosine-derived compound. 相似文献