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101.
Zusammenfassung Mit Hilfe eines einfachen quantenmechanischen Näherungsansatzes wird versucht, Bindungsabstände und Normalfrequenzen des Hydrogendifluoridions sowie des entsprechenden deuterierten Ions zu berechnen. Hierbei wird die Elektronenwechselwirkung der beiden Fluoridionen untereinander durch einen der Statistik entlehnten Ausdruck berücksichtigt. Die Methode liefert für die Abstände gute, für die Normalfrequenzen durchaus befriedigende Ergebnisse.
Der Deutschen Forschungsgemeinschaft danken wir für die Gewährung eines Stipendiums an Karl Hensen. 相似文献
On the basis of a quantum mechanical treatment the bond distances and the normal frequences of the hydrogen difluoride ion and its deuterated analogue are calculated. The electronic interaction of the two fluoride ions is approximated by a statistical calculation. The results are in fairly good agreement with the experimental values.
Résumé Sur la base d'un traitement quantique simple, le calcul des distances de liaison et des fréquences normales est tenté pour l'ion de bifluorure d'hydrogène et son analogue deutéré. L'intéraction électronique des deux ions fluorures est approximée au moyen d'un calcul statistique. Les résultats sont en très bon accord avec les valeurs expérimentales.
Der Deutschen Forschungsgemeinschaft danken wir für die Gewährung eines Stipendiums an Karl Hensen. 相似文献
102.
Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)Co(III)(py)(2) proceeds via the monopyridine complex (Cor)Co(III)(py) to give in each case the unligated cobalt(II) corrole [(Cor)Co(II)](-). In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)Co(III)(py)(2)](+). 相似文献
103.
Density functional theory and complete active space self-consistent field computations are applied to elucidate the singlet diradical character of square planar, diamagnetic nickel complexes that contain two bidentate ligands derived from o-catecholates, o-phenylenediamines, o-benzodithiolates, o-aminophenolates, and o-aminothiophenolates. In the density functional framework, the singlet diradical character is discussed within the broken symmetry formalism. The singlet-triplet energy gaps, the energy gained from symmetry breaking, the spin distribution in the lowest triplet state, and the form of the magnetic orbitals are applied as indicators for the singlet diradical character. Moreover, a new index for the diradical character is proposed that is based on symmetry breaking. All symmetry breaking criteria show that the complexes obtained from o-catecholates and o-benzodithiolates have the largest and the smallest singlet diradical character, respectively. The singlet diradical character should be intermediate for the complexes derived from o-phenylenediamines, o-aminophenolates, and o-aminothiophenolates. The diradical character of all complexes suggests the presence of Ni(II) central atoms. This is also indicated by the d-populations computed by means of the natural population analysis. 相似文献
104.
105.
We compute the Hofer distance for a certain class of compactly supported symplectic diffeomorphisms of 2n. They are mainly characterized by the condition that they can be generated by a Hamiltonian flow
H
t
which possesses only constantT-periodic solutions for 0 <T 1. In addition, we show that on this class Hofer's and Viterbo's distances coincide. 相似文献
106.
Martin Anderle Herwig Schweng Karl E. Kürten Karl W. Kratky 《Journal of statistical physics》1995,81(3-4):843-849
We present evidence that the performance of the traditional fully connected Hopfield model can be dramatically improved by carefully selecting an information-specific connectivity structure, while the synaptic weights of the selected connections are the same as in the Hopfield model. Starting from a completely disconnected network we let genuine Hebbian synaptic connections grow, one by one, until a desired degree of stability is achieved. Neural pathways are thus fixed notbefore, butduring the learning phase. 相似文献
107.
We consider real-space renormalization group transformations for Ising-type systems which are formally defined by $$\exp \left[ { - H'(\sigma ')} \right] = \sum\limits_\sigma {T(\sigma ,\sigma ')} \exp \left[ { - H(\sigma )} \right]$$ whereT(σ, σ′) is a probability kernel, i.e., ∑σ′ T(σ,σ′) = 1 for every configuration σ. For each choice of the block spin configuration σ′, let σ′, let μσ′ be the measure on spin configurations σ which is formally given by taking the probability of σ to be proportional toT(σ, σ′) exp[?H(σ)]. We give a condition which is sufficient to imply that the renormalized HamiltonianH′ is defined. Roughly speaking, the condition is that the collection of measures μσ′ is in the high-temperature phase uniformly in the block spin configuration σ′. The proof of this result uses methods of Olivieri and Picco. We use our theorem to prove that the first iteration of the renormalization group transformation is defined in the following two examples: decimation with spacingb = 2 on the square lattice with β < 1.36β c and the Kadanoff transformation with parameterp on the trian gular lattice in a subset of the β,p plane that includes values of β greater than β c . 相似文献
108.
One-parameter semigroups occurring in operator-limit distributions are investigated. The topological-algebraic background of the relevant monoids is discussed and Lie semigroup theory is applied to the Urbanik Decomposability Semigroup. 相似文献
109.
110.