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81.
Claudio Tavagnacco Gabriele Balducci Giacomo Costa Karl Tschler Wolfgang von Philipsborn 《Helvetica chimica acta》1990,73(5):1469-1480
In four series of strictly related organocobalt complexes, derived from cobaloximes by replacement of the O…H…O with O…-BF2…O and/or (CH2)3 groups, the trends of 59Co-NMR shielding and electrochemical data are discussed. A largely parallel behaviour of the plots of E1/2(I) values for the first Co(III)/Co(II) electron transfer vs. the 59Co chemical shifts reflects the similar sensitivity of the two parameters to a change in electron affinity of the central metal ion due to a variation of the organic group R. E1/2(II) values for the second Co(II)/CO(I) electron transfer are less sensitive to the change of R, but the trend of the plot vs. δ(59Co) is still parallel in the four series. Consistent deviations from a roughly linear dependence of E1/2(I) on pKa of the hydrocarbon acid corresponding to R, on Taft constant s?* and on 59Co shielding are noticed for the isopropyl derivatives and attributed to a steric effect. This was confirmed in a series of R? Co(DMG)pyridine complexes in which 59Co shielding decreases steadily with increasing steric parameter Es (Taft) of the alkyl group. There is experimental evidence from X-ray data that δ(59Co) decreases with an increase of the Co? C bond length, illustrating steric hindrance in alkyl coordination to be responsible for the decreased shielding of the 59Co nucleus. The relative displacements of the graphic displays for the different series reflect the effect of changes in electron affinity of the redox center, due to the equatorial ligand, which, in turn, is caused by variations in the electron-withdrawing power due to the introduction of the BF2 group and by the change from ?2 to ?1 valence of the (CH2)3-capped ligands. 相似文献
82.
Various levels of approximation (Hartree-Fock, configuration interaction and double-configuration Hartree-Fock method) are compared for extensive and limited exponent optimization of the atomic orbitals of the wavefunctions. The potential energy curves for the lowest-lying 1
u, 3
u, 1
g, 3
g states of the hydrogen molecule are presented. The shapes of the curves on the highest level of approximation, i.e. with the optimal double-configuration wavefunction, are basically in agreement with previous, more sophisticated and time-consuming work. The influence of the various approximations is also studied for several one-electron properties: charge distribution of the wavefunction along and perpendicular to the molecular axis, quadrupole moment and core attraction energy distribution. Differences arise to the work of Zemke et al. [1], who used a limited exponent optimization with a larger basis set, in the
g states where the orbitals are very diffuse. The differences concern magnitude and location of minima and maxima of potential curves, as well as considerable changes in one-electron properties which depend strongly on the spatial distribution of the orbitals.
On leave to: Institut für Theoretische Chemie, Universität Stuttgart.
On leave to: Office of Computing Activities, National Science Foundation, Washington, D.C. 相似文献
Zusammenfassung Verschiedene Approximationsstufen (Hartree-Fock, Konfigurationenwechselwirkung und Doppelkonfigurationen-Hartree-Fock-Methode) werden für ausgedehnte und begrenzte Exponentenoptimisierung von Atomorbitalen der Wellenfunktionen verglichen. Die Potentialkurven für die niedrigsten 1 u, 3 u, 1 g, 3 g Zustände des Wasserstoffmoleküls werden angegeben. Die Form der Kurven im Rahmen der besten Näherung, d. h. mit Doppelkonfiguration, stimmen im wesentlichen mit früheren aufwendigeren Rechnungen überein. Der Einfluß der verschiedenen Approximationen wird auch an einigen Einelektroneneigenschaften studiert: Ladungsverteilung der Wellenfunktion längs und senkrecht zur Molekülachse, Quadrupolmoment und Verteilung der Rumpfenergie. Unterschiede erscheinen zur Arbeit von Zemke et al. [1], die einen größeren Basissatz mit begrenzter Optimisierung verwandten, bei den g Zuständen, wo die -Orbitale sehr diffus sind. Die Unterschiede betreffen Größe und Lage der Minima und Maxima der Potentialkurven sowie beträchtliche Änderungen in solchen Einelektroneneigenschaften, die stark von der räumlichen Verteilung der Orbitale abhängen.
Résumé Comparaison de différents niveaux d'approximation (Hartree-Fock, interaction de configuration et Hartree-Fock à deux configurations) pour des optimisations étendues et limitées des orbitales atomiques de base. Calcul des courbes d'énergie potentielle pour les plus bas états 1 u, 3 u, 1 g, 3 g de la molécule d'hydrogène. Pour la fonction d'onde la plus raffinée: H.F. à deux configurations, la forme des courbes est en accord avec les résultats obtenus dans des travaux précédents plus complexes et plus coûteux. On étudie aussi l'influence des diverses approximations sur plusieurs propriétés monoélectroniques: distribution de charge le long de l'axe moléculaire et perpendiculairement à celui-ci, moment quadrupolaire et distribution de l'énergie d'attraction de coeur. On trouve des différences avec le travail de Zemke et al. (1), qui utilisent une plus grande base partiellement optimisée, pour les états g où les orbitales sont très diffuses. Les différences concernent la grandeur et la position des extrema des courbes de potentiel, ainsi que des variations importantes des propriétés monoélectroniques qui dépendent fortement de la distribution spatiale des orbitales.
On leave to: Institut für Theoretische Chemie, Universität Stuttgart.
On leave to: Office of Computing Activities, National Science Foundation, Washington, D.C. 相似文献
83.
84.
Coleman KS Bailey SR Fogden S Green ML 《Journal of the American Chemical Society》2003,125(29):8722-8723
Single-walled carbon nanotubes have been cyclopropanated under Bingel reaction conditions, and the functionalized nanotubes have been characterized by atomic force microscopy using "chemical tagging" techniques. 相似文献
85.
We use the nonlocal linear hydrodynamic constitutive model, proposed by Evans and Morriss [Statistical Mechanics of Nonequilibrium Liquids (Academic, London, 1990)], for computing an effective spatially dependent shear viscosity of inhomogeneous nonequilibrium fluids. The model is applied to a simple atomic fluid undergoing planar Poiseuille flow in a confined channel of several atomic diameters width. We compare the spatially dependent viscosity with a local generalization of Newton's law of viscosity and the Navier-Stokes viscosity, both of which are known to suffer extreme inaccuracies for highly inhomogeneous systems. The nonlocal constitutive model calculates effective position dependent viscosities that are free from the notorious singularities experienced by applying the commonly used local constitutive model. It is simple, general, and has widespread applicability in nanofluidics where experimental measurement of position dependent transport coefficients is currently inaccessible. In principle the method can be used to predict approximate flow profiles of any arbitrary inhomogeneous system. We demonstrate this by predicting the flow profile for a simple fluid undergoing planar Couette flow in a confined channel of several atomic diameters width. 相似文献
86.
Summary For a classC of structures there are two archetypical questions: 1) Is every group G the full automorphism group of some C C? and 2) May every C C embedded into some homogeneous H C, i.e. into a structure H enjoying some transitivity properties? Using model theoretic language and conditions on the existence of certain free constructions withinC, some rather general positive answers to these questions are obtained. These abstract results give some (methodical) unification to a variety of theorems for some very concrete classesC of combinatorial, geometrical or algebraic nature in the literature. To underline this point, the major part of the paper is devoted to a systematic survey of classesC of structures in which our general approach is applicable, included many classesC for which our type of questions has not yet been considered.
Unserem lieben FreundeAdriano Barlotti zum 60. Geburtstag gewidmet.
Die Autoren danken herzlich der Deutschen Forschungsgemeinschaft für die gewährte Unterstützung; der erstgenannte Autor bedankt sich darüber hinaus beim Consiglio Nazionale delle Ricerche für ein Stipendium an der Universität Bologna. 相似文献
Unserem lieben FreundeAdriano Barlotti zum 60. Geburtstag gewidmet.
Die Autoren danken herzlich der Deutschen Forschungsgemeinschaft für die gewährte Unterstützung; der erstgenannte Autor bedankt sich darüber hinaus beim Consiglio Nazionale delle Ricerche für ein Stipendium an der Universität Bologna. 相似文献
87.
Karl Wisseroth 《Colloid and polymer science》1959,166(1):14-19
Summary In this paper the best available inorganic insecticides were chosen as emulsifying agents. While preparing the emulsions it
was kept in mind to take minimum of the substance as an economical measure. The ratio of water to oil was so kept, as to have
the most stable and mobile emulsion, in order that it could be easily-used for practical purposes. It was found that the percentage
of 0.5 and 0.25 of the emulsifying agent with a ratio of oil to water as 20∶80, best stable emulsions are produced. The substances
taken were copper arsenate and arsenite, lead, calcium and aluminium arsenates. With the addition of natural colloids, the
stability is increased to a great extent. The natural colloids easily formed a highly solvated membrane which envelops the
oil globules, thereby making the emulsions very stable. The addition of soaps deteriorates or breaks the emulsions in all
cases, but with aluminium arsenate. The addition of soaps instead of having an antagonistic effect, re-inforces aluminium
arsenates. The aluminium arsenate is hydrolysed producing aluminium hydroxide. It has already been seen by previous workers
that aluminium hydroxide and sodium or potassium oleate act as very good emulsifying agents.
Zusammenfassung Die erreichbaren anorganischen Insektizide werden als emulgierende Agentien untersucht. Es wurde bei der Emulsion angestrebt, als m?gliches ?konomisches Ma? mit einem Minimum an Substanzen auszukommen. Das Verh?ltnis von Wasser zu ?l wurde so gew?hlt, da? m?glichst stabilste und flüssige Emulsionen erreicht wurden, so da? leichte Anwendbarkeit für praktische Zwecke besteht. Ein Gehalt an 0,5 und 0,25% und ein Verh?ltnis ?l zu Wasser wie 20 zu 80 ergab die stabilsten Emulsionen. Es wurden Kupferarsenat und -arsenit Blei-, Calzium- und Aluminiumarsenate verwendet. Zufügung von natürlichen Kolloiden verst?rkte die Stabilit?t au?erordentlich. Die natürlichen Kolloide bilden hochsolvatisierte Membranen, die die ?ltr?pfchen einhüllen und so die Stabilit?tserh?hung bedingen. Die Zufügung von Seifen zerst?rt oder bricht die Emulsionen, au?er im Falle von Aluminiumarsenat. In diesem Falle wird der Effekt statt dessen verst?rkt. Al-Arsenat wird hydrolysiert, es entsteht Al-Hydroxyd. Schon von anderer Seite wurde gezeigt, da? Al-Hydroxyd mit Na- oder K-Oleat sehr gut emulgierend wirkt.相似文献
88.
Localized molecular orbitals, two- and three-center bond indices of 1,5-dicarba-closo-pentaborane ( 5 ) and 1,5-dicarba-closo-pentaborane ( 3 ) and their hydrocarbon analogs bicyclo [1,1,1]-pentane and [1,1,1] propellane, respectively, have been calculated using a suitable basis set. No previously reported three-center CBC bond has been found. However, a new three-center BCB bond has been observed in 1,5-dicarba-closo-pentaborane ( 5 ). © 1995 John Wiley & Sons, Inc. 相似文献
89.
Heinz Falk Karl Grubmayr Martha Marko 《Monatshefte für Chemie / Chemical Monthly》1989,120(8-9):771-779
Summary A violinoid and a 2,3-dihydrobilindione chromophore is attachedvia an appendix anchored at rings A of the pigments by means of reacting them with the polyacryl-N-acryloxysuccinimid copolymer to yield water-soluble chromopolymers. They are characterized by a molecular mass of about 4000 to 6000 and a relation of one chromophoric unit per 6 to 22 monomers. Their absorption spectra and circular dichroism recorded in water and dimethylsulfoxide as solvents are discussed with respect to structural aspects, and in comparison with monomeric chromophore derivatives.
Herrn Prof. Dr. K. Schlögl mit den besten Wünschen zum 65. Geburtstag gewidmet 相似文献
90.
The enantiomers of the 2,3-dihydrobilatriene-abc1 have been separated by recycling chromatography on triacetylcellulose. Comparison of their chiroptical properties with those of amino acid substituted analogues, like3, reveals the chirality of center 3 to be of minor influence on the values. Stabilization of a definite helical conformation of these pigments seems to depend on this influence together with an appropriate dipole-dipole interaction. 相似文献