Electronic Origin of the Structural Anomalies of Zinc and Cadmium
Wedig, Ulrich and Nuss, Hanne and Nuss, Jürgen and Jansen, Martin and Andrae, Dirk and Paulus, Beate and Kirfel, Armin and Weyrich, Wolf – 2013
The electron distributions in position and in momentum space of the hcp metals magnesium and zinc are investigated experimentally and compared to results of quantum‐chemical calculations. Furthermore, a survey is given on recent analyses of the bonding properties of zinc and cadmium, using the method of increments. The experimental deformation densities were obtained by refining multipole models to X‐ray diffraction data sets measured at 100 K with either Mo‐Kα (Mg) or Ag‐Kα (Zn) radiation. The final RF values (Valray/Jana2006) are 0.0028/0.0034 (Mg) and 0.0068/0.0068 (Zn). The differences to deformation densities obtained from periodic density functional calculations are discussed. The effect of dynamical electron correlation on the electron density was analyzed, using cluster models. Compton profiles were measured with 88.67 keV synchrotron radiation at beamline ID15B at the ESRF in Grenoble. Varied orientations of the samples allowed for probing the projected momentum distribution along the ,  and  directions. Fourier transforms of the computed reciprocal form factor B(r) resulted in the corresponding theoretical Compton profiles. It is suggested that the anomalous hcp structure of zinc is favored by a kinetic balancing of the valence electrons, i.e. correlation mediated 4s‐3d interactions.