The electronic structure of CuCl: An “ab initio” Hartree-Fock SCF-MO study of the CuCl43− cluster

Results from restricted Hartree-Fock SCF-MO calculations on the CuCl₄^3? cluster occurring in solid CuCl are reported. The chemical bonding is discussed on the basis of a population analysis of the ground state orbitals. Calculations on the first ionized states show the Cu 3d electrons to be less tightly bound than the Cl 3p electrons in contrast to Koopmans' theorem predictions and in agreement with experiment. The high degree of localization of the 3d hole orbitals obtained is in conflict with earlier estimates of d-bond covalency. It is suggested that the “Ham effect” rather than covalency is responsible for the reduced spin orbit splitting that can be deduced from the observed exciton absorption. The potential surface for a Cu⁺ ion moving in the field of neighbouring Cl^? ions, has been determined from calculations on the CuCl₄^3? cluster in which the metal ion has been displaced towards a face, an edge or a vertex of the surrounding tetrahedron. The vibration frequency and the activation energy for the diffusion of Cu⁺ ions obtained are in fair agreement with the experimental data. These results support the viewpoint that the anomalous change in scattering intensity with temperature observed in X-ray and neutron diffraction studies is due to the presence of a substantial fraction of the Cu⁺ ions on interstitial lattice sites.     

Increased melanogenesis is a risk factor for oxidative DNA damage--study on cultured melanocytes and atypical nevus cells

Melanin synthesis is an oxygen-dependent process that acts as a potential source of reactive oxygen species (ROS) inside pigment-forming cells. The synthesis of the lighter variant of melanin, pheomelanin, consumes cysteine and this may limit the capacity of the cellular antioxidative defense. We show that tyrosine-induced melanogenesis in cultured normal human melanocytes (NHM) is accompanied by increased production of ROS and decreased concentration of intracellular glutathione. Clinical atypical (dysplastic) nevi (DN) regularly contain more melanin than do normal melanocytes (MC). We also show that in these cultured DN cells three out of four exhibit elevated synthesis of pheomelanin and this is accompanied by their early senescence. By using various redox-sensitive molecular probes, we demonstrate that cultured DN cells produce significantly more ROS than do normal MC from the same donor. Our experiments employing single-cell gel electrophoresis (comet assay) usually reveal higher fragmentation of DNA in DN cells than in normal MC. Even if in some cases the normal alkaline comet assay shows no differences in DNA fragmentation between DN cells and normal MC, the use of the comet assay with formamidopyrimidine DNA glycosylase can disclose that the DNA of the cultured DN cells harbor more oxidative damage than the DNA of normal MC from the same person.     

Tetrameric copper(II) halide compounds containing (R,S)- and (S)-1-amino-2-propanolate ions

Summary Compounds with the composition CuXL, in which X=Cl^– or Br^– and L=R,S-1-amino-2-propanol andS-1-amino-2-propanol, both with deprotonated hydroxy groups, are described. Magnetic measurements strongly suggest these compounds to have a tetrameric cubane-type structure with a Cu₄O₄ core. The racemic and optically-active compounds show a different magnetic behaviour, most likely originating from different cluster types for the isomers. The results of the i.r., f.i.r. and e.s.r. spectra are in good agreement with the proposed cluster types.     

Chemical lasers II

A short survey is given of population inversions resulting from chemical reactions. The way in which the possibilities for realisation of a chemical laser are investigated by us is discussed and the results obtained are given.     

Broken orbital-symmetry and the description of hole states in the tetrahedral [CrO4]− anion. I. Introductory considerations and calculations on oxygen 1s hole states

The localization of holes in systems containing spatially equivalent sites is discussed in terms of a simple one-particle model in which quantum mechanical delocalization effects compete with essentially classical polarization or dielectric relaxation effects. The predictions of the model for a tetrahedral system like CrO^?₄ compare favourably with the results of symmetry unrestricted SCF calculations on O_1s hole states. The connection with a Cl treatment using symmetry-restricted MOs is discussed. The calculated ionization energies are finally compared with XPS measurements on Na₂CrO₄. To this end the crystal surrounding of the CrO^?₄ anion has been represented by a point charge model and the ensuing Modelung field was included in the SCF calculations. In contrast to the Td restricted result of 551.4 eV, the completely localized C_3v results of 532.6 eV is in satisfactory agreement with the experimental data which are found around 530.0 eV.     

Chemical lasers I

The concept of a chemical laser is discussed and a preferable definition is proposed. In order to obtain some insight into the feasibility of chemical pumping in general and into the orders of magnitude of the parameters involved, the consequences of a simple model, more or less related to a stationary flamelaser, are explored.According to this model i) a lower limit depending on flow velocity and wavelength exists for the rate at which production and radiative processes may proceed, and ii) the available gain can very appreciably exceed the critical value needed for laser action if certain conditions are satisfied.The assumptions underlying the model and its results, and their applicability in practice are briefly discussed.     

Size of the freeze-out source in high energy heavy ion collisions

Based on a hydro-inspired azimuthally symmetric emission function, we analyze the HBT radius Rs and the single-particle transverse momentum spectra in Au+Au collisions measured by the STAR Collaboration at SNN = 200 GeV. The results show that consistent assumptions about transverse density (and/or flow profile) in the calculation of the HBT radius Rs and single-particle spectral analyses play an important role for understanding the size of the freeze-out source.     

Generalized Bethe-Goldstone calculations on molecules

Computer programs have been developed in order to apply Nesbet's method of generalized Bethe-Goldstone equations to the calculation of electronic correlation effects in molecules. After an outline of the method some preliminary results for H₂O and BH are presented.     

Relativistic and electron correlation effects on thed-d spectrum of transition metal fluorides

Summary The electronic spectra of the transition metal complexes CoF ₆ ^2– , RhF ₆ ^2– and IrF ₆ ^2– that occur in the solids Cs₂MeF₆ are calculated. Hartree-Fock and Dirac-Fock calculations followed by non-relativistic and relativistic CI calculations respectively are used to study the influence of relativity and electron correlation. The calculated transitions are found to agree fairly well with experiment, the largest discrepancies arising from the neglect of differential dynamical electron correlation effects.