Farbzentren rhombischer und monokliner Symmetrien in NaF

A number of zero-phonon absorption lines ofF aggregate color centers is studied inx-irradiated NaF crystals under uniaxial stress. The color centers associated with the lines are found to exhibit rhombic (D_2h, D₂, C_2v; rotation axes along 〈110〉 and 〈100〉) and monoclinic (C_2h, C₂, C_s; rotation axis along 〈110〉) symmetries. The transitions of the rhombic color centers correspond to 〈100〉 and 〈110〉 dipoles, those of the monoclinic centers to 〈112〉 and 〈110〉 dipoles. The most prominent line at 5803 Å is due to a 〈112〉 dipole transition within a monoclinic color center. Several models of centers are discussed.     

Ein Verfahren zur Untersuchung kleiner Mengen von schwach aktiven Stoffwechselprodukten

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Polymerization of hexamethylcyclotrisiloxane with a biscatecholsiliconate. I. Nature of polymerization

Polymerization behavior of hexamethylcyclotrisiloxane (D₃) in toluene solution with the use of benzyltrimethylammonium bis(o-p;henylenedioxy)phenylsiliconate as a catalyst, dimethyl sulfoxide as promoter, and adventitious moisture as initiator was investigated. The polymerization system gives a linear difunctional polymer, HO(Me₂SiO)_xH, with a molecular weight which is inversely proportional to the amount of water reacted rather than to the amount of catalyst employed. The polymerization in the presence of H₂O gives rise to molecular weight distributions very close to Poisson distributions. The normalized experimental GPC curve agrees very well with the theoretical GPC curve calculated from the polymerization scheme: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm H}_2 {\rm O} + ({\rm Me}_2 {\rm SiO})_3 \to {\rm HO}({\rm Me}_2 {\rm SiO})_3 {\rm H}} \\ {{\rm HO(Me}_{\rm 2} {\rm SiO)}_{\rm 3} {\rm H} + {\rm N(Me}_{\rm 2} {\rm SiO)}_{\rm 3} \to {\rm HO}({\rm Me}_2 {\rm SiO})_{3(n + 1)} {\rm H}} \\ \end{array} $$\end{document} Polymerization carried out in the combined presence of H₂O and ROH, where R is Me or Me₃Si, gives rise to bimodal molecular weight distributions. The resulting polymers consist of HO(Me₂SiO)_2xH and RO(Me₂SiO)_xH. The molecular weight of the former is twice that of the latter, and their proportion depends on the ratio of H₂O to ROH. The system is a special type of “living” polymer.     

Polymerization of Cyclosiloxanes. I. Kinetic Studies on Living Polymer—Octamethylcyclotetrasiloxane Systems

The kinetics of the anionic polymerization of octamethylcyclotetrasiloxane (D₄) initiated by α-methylstyrene living polymer in tetrahydrofuran was studied. The following kinetic scheme was postulated: Initiation: Propagation: where S^- and M represent the initiator and D₄, respectively. At a living end concentration of 0.0377 mole/l. and a monomer concentration of 1.5 mole/l. in tetrahydrofuran at 25°C. the following kinetic data were obtained: k₁ = 2.3 × 10^?4 l./mole-sec., k₂ < 2.3 × 10^?5 sec.^?1, k₃ = 2.75 × 10^?2l./mole-sec. k₄ ≈ 1.17 × 10^?2 sec.^?1, K₁ > 10 l./mole and K₂ ≈ 2.35 l./mole. The rate constants k₁ and k₃ were found to be dependent on the concentration of anions. This is attributed to the dissociation of ion pairs to free ions at lower concentration. Under the experimental conditions studied the majority of the anions were present in the form of ion pairs. The reactivity of the free ions is about 100 times greater than that of ion pairs. There is no temperature effect on K₂, indicating zero ΔH and positive ΔS in the propagation reaction.     

Pseudo Stark and uniaxial stress splitting of the 6955 Å zero-phonon line in LiF

The spectral resolution of quartz crystals bent to a cylindrical form by means of four rods was investigated with CuKα radiation in a reflection type arrangement. The crystal adjustment was made optically using interference fringes. With the crystal bent to a circular cylinder the deviations from exact focusing inherent to the Johann case could be measured and were found to be in agreement with theory. — Crystals bent to a logarithmic spiral have also been studied. With a 24 mm broad reflecting area (mean radius of curvature 1 m; (13¯40)-plane) an uncorrected full width at half maximum intensity of 0.43 XU or 2.25 eV was observed for the CuKα ₁ line, in agreement with double crystal spectrometer measurements.     

Untersuchung von Getreide, Mehl und Mehlprodukten

Ohne Zusammenfassung