Beiträge zur Chemie der Pyrrolpigmente, 38. Mitt.: Zur Assoziation von Gallenpigmenten

The long standing problem of solvent dependent absorption spectra of certain bile pigments such as bilirubindimethylester has been solved by measurement of molecular masses by means of vapour pressure osmometry. Using this method and the investigation of the concentration and temperature dependence of the absorption spectra on several model compounds an association equilibrium for pigments of the rubinoid structural type could be confirmed. Moreover the optical properties of the coexisting species and the corresponding equilibrium constants could be deduced by spectroscopic techniques. Verdinoid pigments lacking free carboxylic functions on the other hand tend to be monomeric in solution. A heteroassociated species involving equimolar amounts of a verdinoid and a rubinoid pigment could be verified existing on adsorbents like silicagel.

37. Mitt.:Falk, H., Thirring, K., Tetrahedron, im Druck.     

Halogenated 3-pyridylketones

The oxidation of 2,6-dichloro-3-benzylpyridines and bis(2,6-dichloro-3-pyridyl)methanes, respectively, was accomplished using chromic trioxide in a highly acidic medium. The synthesis of several phenyl-3-(2,6-dichloropyridyl)ketones and of bis(2,6-dichloro-3-pyridyl)ketone are reported.     

Perturbed sites and host—guest—host exciton cascade in the biphenyl isotopic mixed crystal phosphorescence

An interesting energy cascade is observed in the phosphorescence spectra of 1% biphenyl-h₁₀ in biphenyl-d₁₀ (2–15 K); strongly perturbed host sites, with energy levels below that of the protonated guest, quench the guest sites at higher temperatures (11–15 K). The identification of the perturbed sites is based on vibrational characteristics (both intensity and frequency), obtained with the help of phosphorescence spectra of biphenyl-h₁₀ and biphenyl-d₁₀ in an argon matrix, indicating an isotope dependent vibronic structure. A partial vibrational analysis is presented, resulting in confirmation of the first triplet state of biphenyl as orbitally ungerade. The dynamics of the triplet excitation are discussed, including several possible mechanisms explaining the non-Boltzmann nature of the low-temperature steady state.     

Ab initio SCF Calculation of the Fluoronium Ion: Geometry,electronic structure and vibrational constants

An ab initio SCF calculation of 42 points of the energy hypersurface of the fluoronium ion is presented using a contracted F(5s/3p), H(2s) gaussian basis set. In its equilibrium structure a bond length of 1.812 a.u. and a HFH bond angle of 127.2° are predicted. The calculated vibrational frequencies for H₂F⁺, HDF⁺, and D₂F⁺ are in good agreement with the experimental data.     

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A New Technique for Preserving Conservation Laws

Foundations of Computational Mathematics - This paper introduces a new symbolic-numeric strategy for finding semidiscretizations of a given PDE that preserve multiple local conservation laws. We...     

Representations of double coset hypergroups and induced representations

The principal goal of this paper is to investigate the representation theory of double coset hypergroups. IfK=G//H is a double coset hypergroup, representations ofK can canonically be obtained from those ofG. However, not every representation ofK originates from this construction in general, i.e., extends to a representation ofG. Properties of this construction are discussed, and as the main result it turns out that extending representations ofK is compatible with the inducing process (as introduced in [7]). It follows that a representation weakly contained in the left-regular representation ofK always admits an extension toG. Furthermore, we realize the Gelfand pair (where are a local field andR its ring of integers) as a polynomial hypergroup on ℕ₀ and characterize the (proper) subset of its dual consisting of extensible representations.     

Über lineare Unabhängigkeit

It is the aim of the present work to prove, under appropriate conditions, lower estimates for the dimension of w ₁ + ... + w _m over , wherew ₁,...,w _m are given real numbers. In particular, if this dimension ism, i.e. ifw ₁,...,w _m are linearly independent over , we are also interested in a quantitative version of this fact. Our qualitative theorems generalize a result of Nesterenko. Its formulation is quite similar to the axiomatization of methods for algebraic independence, as it became usual during the last decade.

     

Jets

This is a discussion of concentrated large-scale flows in planetary atmospheres and oceans, argued from the viewpoint of basic geophysical fluid dynamics. We give several elementary examples in which these flows form jets on rotating spheres. Jet formation occurs under a variety of circumstances: when flows driven by external stress have a rigid boundary which can balance the Coriolis force, and at which further concentration can be caused by the beta effect; when there are singular lines like the line of vanishing windstress or windstress-curl, or the Equator; when compact sources of momentum, heat or mass radiate jet-like beta plumes along latitude circles; when random external stirring of the fluid becomes organized by the beta effect into jets; when internal instability of the mass field generates zonal flow which then is concentrated into jets; when bottom topographic obstacles radiate jets, and when frontogenesis leads to shallow jet formation. Essential to the process of jet formation in stratified fluids is the baroclinic life cycle described in geostrophic turbulence studies; there, conversion from potential to kinetic energy generates eddy motions, and these convert to quasibarotropic motions which then radiate and induce jet-like large-scale circulation. Ideas of potential vorticity stirring by eddies generalize the notion of Rossby-wave radiation, showing how jets embedded in an ambient potential vorticity gradient (typically due to the spherical geometry of the rotating planet) gain eastward momentum while promoting broader, weaker westward circulation. Homogenization of potential vorticity is an important limit point, which many geophysical circulations achieve. This well-mixed state is found in subdomains of the terrestrial midlatitude oceans, the high-latitude circumpolar ocean, and episodically in the middle atmosphere. Homogenization expels potential vorticity gradients vertically to the top and bottom of the fluid, and sideways to the edges of flow domains or gyres; in both these ways is jet formation enhanced.