Untersuchungen an Systemen aus Salzen und gemischten Lösungsmitteln. VI. Das Verhalten des reziproken Salzpaares Na2SO4 + 2 KCl ⇌ K2SO4+2 NaCl in Methanol-Wasser-Mischungen

The solubility isotherms of the system Na₂SO₄? K₂SO₄? CH₃OH? H₂O at 25,40 and 55°C and the solubilities in the system of the metathetic salt reaction Na₂SO₄+ + 2KCl ? K₂SO₄ + 2NaCl in methanol-water mixtures at 10 and 25°C have been determined and the nature of the solid phases established. The addition of methanol causes an enlargement of the sulphatic existence fields. A flow sheet for the industrial application of the results is communicated.     

Critical behavior of betaine arsenate

The critical exponents , and of undeuterated and partially deuterated ferroelectric betaine arsenate are estimated. Small but remarkable deviations from the tricritical values are observed. The obtained values are tested via scaling of the isothermals.At some distance aboveT _c a cross-over of the effective critical exponent to a value typically for short-range forces is observed. A suitably defined cross-over temperature range decreases with increasing deuteration and seems to vanish near the antiferroelectric phase boundary.     

Analysis of functional groups on the surface of plasma-treated carbon nanofibers

Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions.     

Møller-Plesset (MP2) perturbation theory for large molecules

Summary A novel formulation of MP2 theory is presented which starts from the Laplace transform MP2 ansatz, and subsequently moves from a molecular orbital (MO) representation to an atomic orbital (AO) representation. Consequently, the new formulation is denoted AO-MP2. As in traditional MP2 approaches electron repulsion integrals still need to be transformed. Strict bounds on the individual MP2 energy contribution of each intermediate four-index quantity allow to screen off numerically insignificant integrals with a single threshold parameter. Implicit in our formulation is a bound to two-particle density matrix elements. For small molecules the computational cost for AO-MP2 calculations is about a factor of 100 higher than for traditional MO-based approaches, but due to screening the computational effort in larger systems will only grow with the fourth power of the size of the system (or less) as is demonstrated both in theory and in application. MP2 calculations on (non-metallic) crystalline systems seem to be a feasible extension of the Laplace transform approach. In large molecules the AO-MP2 ansatz allows massively parallel MP2 calculations without input/output of four-index quantities provided that each processor has in-core memory for a limited number of two-index quantities. Energy gradient formulas for the AO-MP2 approach are derived.Dedicated to Prof. W. Kutzelnigg whose books on theoretical chemistry aroused my interest in this field     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XIV. Untersuchungen über Benzylwolframverbindungen-Darstellung und Charakterisierung des Wolframtetrabenzyls

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XIV. Investigations on Benzyl Tungsten Compounds. – On the Formation and Characterization of Tetrabenzyl Tungsten Unstable benzyl tungsten pentachloride is formed from tribenzyl boron and tungsten hexachloride. Other benzylating agents yield only less defined reduction products. – Reacting WCl₄ · 2 THF with dibenzyl magnesium W(CH₂C₆H₅)₄ can be obtained. The new compound is stable at room temperature and is thoroughly characterized.     

Exploiting non-abelian point group symmetry in direct two-electron integral transformations

Summary A simple and general scheme to exploit any discrete point group symmetry in two-electron integral transformations is introduced. It has been implemented together with integral pre-screening techniques in direct two-electron integral transformations. Its application has also been extended to subsequent MO integral processing steps like MP2 or solution of the coupled-perturbed Hartree-Fock equations (CPHF). Timings for representative applications are presented.     

Hybrid extension of Schottky space

Part of this work was written while the author was feliow of the Graduiertenkolleg Geometrie und Mathematische Physik at the University of Bochum, Germany.     

Investigations on the determination of NO2 with galvanic nitrate solid electrolyte cells

Solid electrolyte cells for detecting NO₂ with Ba(NO₃)₂ or Sr(NO₃)₂ partially replaced by -Al₂O₃ as solid electrolytes have been studied. The cell tension depends on the NO₂- as well as on the NO-concentration. Investigations of the establishment of the NO₂-NO-O₂-equilibrium by the catalytic effects of the used electrode materials Pt and Au have shown that a decomposition of NO₂ below 400°C cannot be expected.17th Communication on oxoanionic solid electrolytes and their possible applications; 16th Communication see Solid State Ionics 51:183–185 (1992)Extension of a part of the lecture of V. Brüser, S. Jakobs, H.-H. Möbius and U. Schönauer Galvanische NO₂-Sensoren mit Nitrat-Festelektrolyten given in Feldberg, 3. 6. 1993