Zur Synthese und Struktur von K3N

Synthesis and Structure of K₃N Two phases in the binary system K/N have been obtained via co‐deposition of potassium and nitrogen onto polished sapphire at 77 K and subsequent heating to room temperature. The powder diffraction pattern of one of these phases can be satisfactorily interpreted by assuming the composition K₃N, and the anti‐TiI₃ structure‐type, which is also adopted by Cs₃O. The resulting hexagonal lattice constants are: a = 779.8(2), c = 759.2(9) pm, Z = 2, P6₃/mcm. Comparison with possible structures of K₃N generated by computational methods and refined at Hartree‐Fock‐ and DFT level, reveals that the energetically most favoured structure has not formed (presumable Li₃P‐type), but instead one of those with very low density. In this respect, the findings for K₃N are analogous to the results on Na₃N. The thermal evolution of the deposited starting mixture has been investigated. Hexagonal K₃N transforms to another K/N phase at 233 K. Its XRD can be fully indexed resulting in an orthorhombic cell a = 1163, b = 596, c = 718 pm. Decomposition leaving elemental potassium as the only residue occurs at 263 K.     

Antiferromagnetism of type II in nonstoichiometric YbP

A polycrystalline smaple of nonstoichiometric ytterbium phosphide, YbP_0.84, was investigated by neutron scattering, Mössbauer spectroscopy and bulk magnetic measurements. Neutron diffraction experiments prove the existence of antiferromagnetic type II ordering belowT _N =0.64 K, in contrast to the observed antiferromagnetic type III ordering in the stoichiometric Kondo-like compounds YbN and YbAs. The temperature dependence of the average ordered magnetic moment per Yb³⁺ ion with saturation value _Yb = 1.03(7) _B is similar to that of YbN. Mössbauer experiments prove the magnetic phase transition to be first order with different regions in the sample having slightly different transition temperatures. By means of inelastic neutron scattering the crystal-field level scheme was established to be ₆ – ₈(19meV) – ₇(43meV).     

Stereoelectronic control of exo/endo rate ratios in the solvolysis of 2-norbornyl p-toluenesulfonates

The variable exo/endo rate ratios observed in the solvolysis of 6-exo-substituted exo- and endo-2-norbornyl p-toluenesulfonates are due to differential transmission of polar effects in the transition state for ionization.     

The Nature of the vibronic intensity borrowing mechanism in the 1B3u(n)1Ag(X) transition of pyrazine

The transition intensities of the S₀S₁ gas phase absorption spectra of pyrazine-d₀ and -d₄ were carefully measured. A discussion of the various aspects of vibronic intensity borrowing for this unique case is presented using our new experimental results.