Calculations on electric-field-induced shifts in ultraviolet absorption spectra: The significance of doubly excited configurations

Calculations on the cation-induced shifts in the UV spectrum of the terphenyl mononegative ion suggest that the spectra of the ions of alternant hydrocarbons, as compared with those of the molecules, are rather insensitive to electric field perturbations. This feature only shows up if one includes enough (doubly) excited configurations to allow for the polarization of the excited states involved in the optical transitions.

---

Zusammenfassung Berechnungen über die von Kationen verursachten Verschiebungen im UV-Spektrum des mononegativen Terphenylions deuten darauf hin, daß die Spektren der Ionen alternierender Kohlenwasserstoffe im Vergleich zu denen der Molekeln gegen vom elektrischen Feld hervorgerufene Störungen ziemlich unempfindlich sind. Dies kommt nur dann zum Ausdruck, wenn man in den Berechnungen genügend (doppelt) angeregte Konfigurationen mit einbezieht, um auch die Polarisation der an den optischen Übergängen beteiligten Anregungszustände zu erfassen.

---

Résumé Des calculs sur les déplacements — provoqués par le cation — dans le spectre ultraviolet de l'ion mononégatif de terphényle indiquent que les spectres des ions d'hydrocarbures alternants, à côté de ceux des molécules, sont assez insensibles aux perturbations du champ électrique. On ne trouve ce résultat que dans le cas où l'on introduit un nombre suffisant de configurations excitées (doublement) pour tenir compte de la polarisation des états excités liés aux transitions optiques.

     

1,3,6-Triphenyl-6-phenylazo-1,4,5,6-tetrahydropyridazin

Base induced 1.4-elimination of pyridine·HI from 1-(2-phenyl-2-phenylhydrazono-ethyl)-pyridinium iodide (6) yields 1.3.6-triphenyl-6-phenylazo-1.4.5.6-tetrahydropyridazine (8) the (4+2)-cyclodimer of the intermediate 1-phenyl-1-phenylazoethylene (7).8 can also be obtained by intramolecular oxidative cyclisation (with KMnO₄) of 1.4-diphenylbutane-1.4-dione bisphenylhydrazone (12). Spectroscopic data (ms,¹H-nmr, uv and ir/Raman) confirm the structure of8.     

Studium des gegenseitigen Einflusses der Bindungen in Thiocyanat-Kupfer(II)-Komplexen mit Methyl- und Dimethylpyridinen mittels Infrarotspektroskopie

The infrared spectra of thiocyanato-copper(II) complexes of the type Cu(NCS)₂ L ₂ with all isomeric picolines and lutidines (L) as well as those of the type Cu(NCS)₂ L ₃ withL=3- and 4-picoline, 3,4- and 3,5-lutidine were measured. The behaviour of the (CN) stretching vibrations of the Cu(NCS)₂ L ₂ complexes led to conclusions on the different kind of coordination of the NCS groups in dependence on the ligandL. The mutually conditioned strength of the Cu–NCS and Cu–N(L) bonds in the equatorial plane, especially in the presence of ligandsL with the steric effect, was determined from the frequency shift of the Cu–NCS and Cu–N(L) stretching vibrations with regard to the vibrations for Cu(NCS)₂(pyridine)₂.

---

---

Mit 1 Abbildung     

Die Massenspektren der Pyrrolidide einiger aliphatisch-alicyclischer Carbonsäuren

The mass spectra of the pyrrolidides of some long-chain carboxylic acids with alicyclic residues attached to their ω-end are discussed and compared with the spectra of the corresponding esters. Fragmentation triggered by the pyrrolidide group generates a series of peaks, which clearly exhibits the size and the structure of the carbon chain.     

Electronic and Steric Influence of Axial and Equatorial Ligands in Vitamin B12 Model Complexes Derived from Cobaloxime: Electrochemical and 59Co-NMR Studies

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 E_1/2(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. E_1/2(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 E_1/2(I) on pK_a 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 E_s (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.     

Non relativistic continuum wave functions for two coulomb centres

We give the continuum wave function solutions to the Schrödinger equation for an electron moving field of two point nuclei, as an expansion in terms of one centre Coulomb wave functions in a prolate elliptical coordinate system. These solutions may be chosen to have a convenient asymptotic behaviour, and tend to the conventional solutions of the Helmholtz equation in the limit that the nuclear charge goes to zero. In symmetric systems, where both nuclei have the same charge the angular wave functions are found to be identical with those occurring in the free case, and the expansion coefficients for the corresponding radial solutions are given for selected values of electron energy and nuclear separation.[/p]     

X-ray diffraction and morphology of crystalline,hard, elastic materials

Summary X-ray diffraction and electron microscopic results on several crystalline polymers which demonstrate elastic properties (polypropylene, Celcon^®, poly-4-methyl-pentene) are reported. Photographic small angle X-ray diffraction techniques provided considerable qualitative information, concerning the morphological features of these elastic materials both as extruded, annealed and during extension. Lamellar thickness, thickness distribution and perfection of lamellae could be estimated. Lateral order features and orientation of the lamellar structures were obtainable from the sharpness and length of the equatorial wide angle diffraction arcs. Electron microscopic results essentially confirm the morphological features postulated on the basis of the X-ray results. These morphological features are discussed in terms of a general structural model which appears consistent with the mechanical properties of these materials.

---

Zusammenfassung Röntgenbeugung und elektronenmikroskopische Daten von einigen kristallinen Polymerprodukten mit elastischen Eigenschaften (Polypropylen, Celcon, Poly-4-methylpenten) werden berichtet. Die photographische Röntgen-Kleinwinkelmethode liefert wichtige qualitative Messungen der morphologischen Struktur dieser elastischen Materialien in den Zuständen sowohl wie hergestellt als auch nach Tempern und während des Dehnungsprozesses. Die Dicke der Lamellen, ihre Dikkenverteilung und die Güte der Lamellen konnten abgeschätzt werden. Die laterale Ordnung und die Orientierung der Lamellen kann aus Weitwinkelbeugungsdaten abgeleitet werden. Die Elektronenmikroskopie bestätigt die Morphologie, die aus Röntgendaten folgt. Ein allgemeines Strukturmodel dieser Morphologie, das im Einklang mit den mechanischen Eigenschaften dieser Produkte steht, wird diskutiert.

     

Über eine zum Kreisproblem verwandte Summe

An equivalent form of the classical circle problem is the unproved conjecture (3) . In this note the corresponding conjecture with _k (.) (the 1-periodic Bernoulli polynomials of orderk2) instead of ₁(.) is settled in an affirmative way (even with =0). Moreover, a generalized sum (6) is estimated by means of an analogue to a classical result due tovan der Corput.     

Atomistic Simulation Study of Calcium,Phosphate and Fluoride Ion Association to the Teleopeptide‐Tails of Collagen – Initial Steps to Biomineral Formation

The attachment of single ions to putative adsorption sites in the tails of collagen fibers is investigated by means of molecular dynamics simulations and discussed with respect to the very early steps of apatite/collagen biomineral formation. Our studies clearly demonstrate an increased flexibility of the tails of the triple‐helical collagen protein. Apart from the termini of the backbone, several side chains were also observed to be freely accessible to ion attachment from aqueous solution. The teleopeptide was systematically scanned for suitable adsorption sites for calcium, phosphate and fluoride ions. Association of these ions was then explored from potential of mean force calculations. The resulting energy profiles reveal a variety of favorable protein‐ion bonds and hint at the suitability of the collagen tails to promote apatite aggregation.