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851.
Exact spin-pairing energies are calculated by direct diagonalization of the relevant ligand field plus interelectronic repulsion matrices for the configurations d
4, d
5, d
6, and d
7 of octahedral transition metal ions. The results are presented in terms of /B as function of = C/B for the range of values =3.0 to 8.0. Comparison with the quantity resulting from a simplified approach in which configuration interaction is neglected or considered on an approximate basis only reveals significant differences. Useful estimates of spin-pairing energies are provided, in addition, on the basis of empirical magnetic and electronic spectral data.
Zusammenfassung Exakte Spinpaarungsenergien für die Konfigurationen d 4, d 5, d 6 und d 7 oktaedrischer Übergangsmetallionen werden durch direkte Diagonalisierung der entsprechenden Matrizen des Ligandenfeldes sowie der Elektronenwechselwirkung berechnet. Die Ergebnisse für /B werden in Abhängigkeit von = C/B für den Wertebereich =3.0 bis 8.0 angegeben. Ein Vergleich mit der Größe , die bei einer vereinfachten Behandlung unter Vernachlässigung oder näherungsweiser Berücksichtigung der Konfigurationswechselwirkung erhalten wird, zeigt auffallende Unterschiede. Nützliche Abschätzungen der Spinpaarungsenergie werden außerdem unter Benutzung empirischer magnetischer und elektronenspektroskopischer Daten erhalten.
Résumé Les énergies exactes de couplage de spin sont calculées par diagonalisation directe du champ de ligand correspondant en plus des matrices de répulsion électronique pour les configurations d 4, d 5, d 6 et d 7 des ions octaédriques des métaux de transition. Les résultats sont présentés en termes de /B en fonction de = C/B dan l'intervalle =3,0 à 8,0. On trouve des différences significatives par comparaison de avec les valeurs résultant d'une approche simplifiée sans interaction de configuration ou avec interaction de configuration approchée. De plus, des estimations des énergies de couplage de spin sont obtenues à partir de données empiriques magnétiques et spectrales.相似文献
852.
Suresh C. Shrivastawa Vikash C. Garg Arun K. Dey 《Fresenius' Journal of Analytical Chemistry》1969,248(5-6):305-306
Summary Eriochromecyanine RC has been used as chromogenic reagent for the photometric determination of rhodium(III) on a micro scale. A coloured Rh(III)-ECRC chelate with
max 530 nm at pH 4.0 (25°C) is formed. A detailed study has been made concerning to characteristics, composition and stability of the chelate. Standard deviation was ±1.17%.
Über die photometrische Bestimmung von dreiwertigem Rhodium mit Eriochromcyanin RC
Zusammenfassung Ergebnisse einer Untersuchung über die Zusammensetzung und Stabilität des Komplexes werden mitgeteilt. Das Absorptionsmaximum liegt bei 530 nm (pH 4,0; 25°C). Bestimmungen konnten mit einer Standardabweichung von ±1,17% durchgeführt werden.相似文献
853.
Catalytic bipotentiometric and biamperometric methods for determining silver(I) with the use of the new manganese(IV)-arsenic(III) indicator reaction catalyzed by iodide ions in the presence of sulfuric acid have been developed. The effects of the sulfuric acid concentration of some ionic species, of the mole ratio of manganese(IV) to arsenic(III) in the solution titrated, and of the titrand temperature, as well as of the current and potential difference, respectively, used for polarization of the indicator electrodes on the conditions for determinations of silver(I) of various concentrations were investigated. The error in the determination of 1.0 g/cm3 silver(I) do not exceed 2%, and the precision of the results is high for both methods. 相似文献
854.
A potentiometric and spectrophotometric investigation on the formation of zinc(II) complexes with Semi-Xylenol Orange (SXO or H(4)L) is reported. In an aqueous solution (mu = 0.1), three 1:1 complex species, MH(2)L, MHL(-), ML(2-), and a 1:2 complex, ML(6-)(2), seem to exist. In a strongly alkaline medium (above pH 12.5) the complexes may dissociate to give zinc hydroxide and L(4-). The formation of a hydroxy complex is not observed. The absorption maxima are at 445 nm (MH(2)L), 466 nm (MHL(-)) and 561 nm (ML(2-)), the molar absorptivities being 2.34 x 10(4), 2.42 x 10(4) and 3.14 x 10(4) 1.mole(-1) .cm(-1) respectively. The formation constants are (at 25 +/- 0.1 degrees ) log K(M)(ML) = 11.84, log K(M)(MHL) = 7.13, log K(M)(MH(2)L) = 2.70, log K(M)(ML(2)) = 16.60. 相似文献
855.
Yu.S. Varshavsky T.G. Cherkasova N.A. Buzina 《Journal of organometallic chemistry》1974,77(1):117-124
The reaction of rhodium(I) carbonyl chloride, [Rh(CO)2Cl]2, with dichromate, cerium(IV) sulfate, hexachloroplatinic acid or p-benzoquinone in aqueous hydrochloric acid proceeds by consumption of 4 equivalents of oxidizing agent per mole or rhodium(I) in accordance with the equation RhI(CO)2 4e + H2O → RhIII(CO) + 2H+ + CO2A “cyclic” oxidation mechanism is suggested. 相似文献
856.
K. Seshadri F. A. Williams 《Journal of polymer science. Part A, Polymer chemistry》1978,16(7):1755-1778
Since poly(methyl methacrylate) is known to depolymerize largely to its monomer when heated, the chemical kinetics in the gaseous diffusion flame produced by this polymer in a fire may coincide with that of burning liquid methyl methacrylate. To test this hypothesis, flat diffusion flames were probed and extinguished adjacent to surfaces of each of these fuels. Profiles of temperature and of concentrations of stable chemical species are reported, as are gas velocities of approach flow required to produce extinction for various oxygen/nitrogen ratios of the stream. Results revealed structural differences attributable to differing thermal properties of the fuels. Many fuel species were observed in the gas phase, their profiles being partially rationalized on the basis of a suggested decomposition mechanism for gaseous methyl methacrylate. Overall kinetic parameters for gasphase combustion, obtained by use of extinction results in a previously developed theory, are nearly the same for the polymer and monomer but appear to differ by amounts exceeding experimental uncertainties. It is suggested that this may be traced to small differences in fuel species leaving the condensed phase which, for the polymer, is covered by a thin, two-phase region. 相似文献
857.
K. Müller R. Henkelmann J. P. Biersack P. Mertens 《Journal of Radioanalytical and Nuclear Chemistry》1977,38(1-2):9-17
The isotopes3He,6Li,7Be and10B exhibit extremely large cross sections, between 1 and 48 kilobarn, for (n, p) or (n, α) reactions with thermal neutrons.
Together with now available extracted thermal neutron fluxes of 10( n·cm−2·sec−1 or more, these reactions present a highly sensitive method of detecting the mentioned light elements in any heavy matrix
material. Through the experimentally determined energy losses of the emitted protons or α-particles, also well resolved depth
profiles can be obtained, as demonstrated here for some relevant examples from semiconductor and fusion technology. 相似文献
858.
A semi-empirical open shell model of sigma bonded systems has been employed to calculate the binding energies for diatomic lithium halides. The repulsion between the atomic cores is taken as the Coulomb repulsion term modified by the presence of electronic cores. This modification has been estimated from the repulsion term in the Rittner potential function. The agreement with the experimental values is quite satisfactory but the extension of the same method to alkali hydrides results in gross discrepancies. The results are discussed in the light of other results. 相似文献
859.
K. Uno M. Makita S. Ooi Y. Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1968,6(2):257-267
Copolymerization of methacrylic esters derived from glycidyl methacrylate and nucleophiles with styrene was carried out. The monomer reactivity ratios of these methacrylic esters were varied with the alkoxy groups of the esters and the solvent used. 相似文献
860.
Professor J. R. Sabin R. E. Harris T. W. Archibald P. A. Kollman L. C. Allen 《Theoretical chemistry accounts》1970,18(3):235-238
Ab initio calculations are carried out on the planar hexamer model of anomalous water using a variety of basis sets. The results are compared to results of similar calculations on free water and water in the ice I-like puckered ring configurations.
Zusammenfassung Es werden ab initio-Rechnungen für das planare Hexamer-Modell von anomalem Wasser unter Verwendung mehrerer BasissÄtze durchgeführt. Die Ergebnisse werden mit Resultaten Ähnlicher Rechnungen über freies Wasser und Wasser in der I-Eis Ähnlichen Konfiguration verzerrter Ringe verglichen.
Résumé Calculs ab initio sur le modèle hexamérique plan de l'eau anormale en utilisant différentes bases. Les résultats sont comparés à ceux de calculs similaires sur l'eau libre et sur l'eau dans une configuration cyclique compacte analogue à celle de la glace I.相似文献