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61.
A systematic study of the bulk and surface geometrical and electronic properties of a series of transition-metal carbides (TMC with TM = Ti, V, Zr, Nb, Mo, Hf, Ta, and W) by first-principles methods is presented. It is shown that in these materials the chemical bonding is strongly covalent, the cohesive energies being directly related to the bonding-antibonding gap although the shift of the center of the C(2s) band related peak in the density of states with respect to diamond indicates that some metal to carbon charge transfer does also take place. The (001) face of these metal carbides exhibits a noticeable surface rumpling which grows along the series. It is shown that neglecting surface relaxation results in very large errors on the surface energy and work function. The surface formation induces a significant shift of electronic energy levels with respect to the corresponding values in the bulk. The extent and nature of the shift can be understood from simple bonding-antibonding arguments and is enhanced by the structural rippling of this surface. 相似文献
62.
Burguera JL Quintana IA Salager JL Burguera M Rondón C Carrero P Anton de Salager R Petit de Peña Y 《The Analyst》1999,124(4):593-599
An on-line time based injection system used in conjunction with cold vapor generation atomic absorption spectrometry and microwave-aided oxidation with potassium persulfate has been developed for the determination of the different mercury species in fish-eggs oil samples. A three-phase surfactant-oil-water emulsion produced an advantageous flow when a peristaltic pump was used to introduce the highly viscous sample into the system. The optimum proportion of the oil-water mixture ratio was 2:3 v/v with a Tween 20 surfactant concentration in the emulsion of 0.008% v/v. Inorganic mercury was determined after reduction with sodium borohydride while total mercury was determined after an oxidation step with persulfate prior to the reduction step to elemental mercury with the same reducing agent. The difference between total and inorganic mercury determined the organomercury content in samples. A linear calibration graph was obtained in the range 0.1-20 micrograms l-1 of Hg2+ by injecting 0.7 ml of samples. The detection limits based on 3 sigma of the blank signals were 0.11 and 0.12 microgram l-1 for total and inorganic mercury, respectively. The relative standard deviation of ten independent measurements were 2.8 and 2.2% for 10 micrograms l-1 and 8.8 and 9.0% for 0.1 microgram l-1 amounts of total and inorganic mercury, respectively. The recoveries of 0.3, 0.6 and 8 micrograms l-1 of inorganic and organic mercury added to fish-eggs oil samples ranged from 93.0 to 94.8% and from 100 to 106%, respectively. Good agreement with those values obtained for total mercury content in real samples by electrothermal atomic absorption spectrometry was also obtained, differences between mean values were < 7%. With the proposed procedure, 22 proteropterous catfish-eggs oil samples from the northwestern coast of Venezuela were measured; while the organic mercury lay in the range 2.0 and 3.3 micrograms l-1, inorganic mercury was not detected. 相似文献
63.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7161-7169
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model. 相似文献
64.
65.
66.
Elías Molins Amílcar Labarta Javier Tejada Amparo Caubet Santiago Alvarez 《Transition Metal Chemistry》1983,8(6):377-380
Summary Magnetic moments and57Fe Mössbauer spectra at room temperature and at liquid nitrogen temperature of polynuclear ligand-bridged iron phthalocyanines, FePcL (L = pyrazine and 4,4-bipyridyl), are reported. The experimental data are in agreement with a pseudo-octahedral environment around the iron(II) cation. Partially oxidized derivatives, FePc(pz)I0.26 and FePc(bipy)I1.06 have been synthesized and their57Fe Mössbauer spectra and magnetic moments within the same temperature range obtained. Oxidation is shown to be metal centred and the iodine is found to be in I– form for FePc(pz)0.26 and as both I– and I
3
–
species for FePc(bipy)I1.06. While the magnetic moment of FePc(pz) increases upon oxidation, the opposite occurs for FePc(bipy). 相似文献
67.
Bañares L Aoiz FJ González-Lezana T Herrero VJ Tanarro I 《The Journal of chemical physics》2005,123(22):224301
Integral cross sections and thermal rate constants have been calculated for the N((2)D)+H(2) reaction and its isotopic variants N((2)D)+D(2) and the two-channel N((2)D)+HD by means of quasiclassical trajectory and statistical quantum-mechanical model methods on the latest ab initio potential-energy surface [T.-S. Ho et al., J. Chem. Phys. 119, 3063 (2003)]. The effect of rotational excitation of the diatom on the dynamics of these reactions has been investigated and interesting discrepancies between the classical and statistical model calculations have been found. Whereas a net effect of reagent rotation on reactivity is always observed in the classical calculations, only a very slight effect is observed in the case of the asymmetric N((2)D)+HD reaction for the statistical quantum-mechanical method. The thermal rate constants calculated on this Potential-Energy Surface using quasiclassical trajectory and statistical model methods are in good agreement with the experimental determinations, although the latter are somewhat larger. A reevaluation of the collinear barrier of the potential surface used in the present study seems timely. Further theoretical and experimental studies are needed for a full understanding of the dynamics of the title reaction. 相似文献
68.
The diamagnetic square planar d(8) complexes [meso-arylcorrolato]copper(III) become paramagnetic upon warming, indicative of the equilibrium between the [corrolato]copper(III) and the [corrolato](+)* copper(II) forms of the complex. [meso-Triphenylcorrolato]copper(III) was structurally characterized and found to be saddled. 相似文献
69.
S. Suarez A. R. Goñi W. Meckbach P. R. Focke 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1987,6(1):55-59
Using a coaxial cylindric electron spectrometer and an electrostatic ion energy analyzer in tandem, a direct measurement of the difference of the energy of convoy peak electron and the electron equivalent ion energy of protons emerging from the downstream surface of C, Au and Al foils is performed in the proton energy range from 60 to 250 keV. This measurement is made possible using the accepted evidence that for a gas target these energies are equal. It is found that also for the beam foil convoy peak electrons, within an experimental average uncertainty of about ±0.1 eV, there is no difference between these energies. If one accepts that the origin of convoy electrons is from inside the solid, the conclusion is that no retardation by the solid surface potential barrier, which is of the order of a few eV, is observed. This is attributed to the strong electron-ion Coulomb interaction which almost completely overshadows the force exerted on the electron by the field of the surface barrier. 相似文献
70.
Pérez-Juste I Graña AM Carballeira L Mosquera RA 《The Journal of chemical physics》2004,121(21):10447-10455
Linear sulfur-carbon chains C(n)S (n=1-6) of astronomical interest were examined by means of several theoretical methods. The three smallest compounds of the series were chosen to evaluate the performance of several computational models, including Hartree-Fock theory, density functional theory with the Becke's three parameter exchange functional and the correlation functional of Lee, Yang, and Parr (B3LYP), and electron-correlated methods (second-order Moller-Plesset perturbation method (MP2), configuration interaction method including single and double excitations (CISD), and quadratic configuration interaction method including single and double excitations (QCISD) in combination with a large variety of basis sets. The systematic comparison between the experiment and theory indicates that the B3LYP/6-311G** method can be considered suitable for the study of the electronic structures of the C(n)S compounds. The electronic ground states of the C(n)S molecules alternate between 1Sigma and 3Sigma for odd and even values of n, respectively. The B3LYP/6-311G** wave functions for these electronic ground states were analyzed by means of the atoms in molecules (AIM) and natural bond orbital (NBO) methods. Both approaches suggest that the electronic structures for the singlet and triplet compounds must be considered separately. According to the NBO method, singlet compounds can be properly represented by acetylenic structures with alternating single and triple bonds (S[triple bond]C-C[triple bond]C...). However, triplet compounds are better described by means of double bond-double bond cumulenic structures (S=C=C=C=C...) as a consequence of the average between different alpha and beta electronic densities. AIM delocalization indexes and NBO interactions between localized orbitals also indicate that these structures are strongly pi delocalized. Finally, the different singlet and triplet structures proposed provide a consistent explanation for the geometries, dipole moments, and spin-density values of the C(n)S compounds studied. 相似文献