Experimental X-ray Charge-Density Studies─A Suitable Probe for Superconductivity? A Case Study on MgB.

Case studies of 1T-TiSe and YBaCuO have demonstrated that X-ray diffraction (XRD) studies can be used to trace even subtle structural phase transitions which are inherently connected with the onset of superconductivity in these benchmark systems. However, the utility of XRD in the investigation of superconductors like MgB lacking an additional symmetry-breaking structural phase transition is not immediately evident. Nevertheless, high-resolution powder XRD experiments on MgB in combination with maximum entropy method analyses hinted at differences between the electron density distributions at room temperature and 15 K, that is, below the of approx.

J(Si,H) Coupling Constants of Activated Si-H Bonds.

We outline in this combined experimental and theoretical NMR study that sign and magnitude of J(Si,H) coupling constants provide reliable indicators to evaluate the extent of the oxidative addition of Si-H bonds in hydrosilane complexes. In combination with experimental electron density studies and MO analyses a simple structure-property relationship emerges: positive J(Si,H) coupling constants are observed in cases where M → L π-back-donation (M = transition metal; L = hydrosilane ligand) dominates. The corresponding complexes are located close to the terminus of the respective oxidative addition trajectory.

J(Si,H) Coupling Constants in Nonclassical Transition-Metal Silane Complexes.

We will outline that the sign and magnitude of J(Si,H) coupling constants provide a highly sensitive tool to measure the extent of Si-H bond activation in nonclassical silane complexes. Up to now, this structure-property relationship was obscured by erroneous J(Si,H) sign determinations in the literature. These new findings also help to identify the salient control parameters of the Si-H bond activation process in nonclassical silane complexes.

Communication: Determination of relativistic effects from X-ray structure factors.

In this communication, a procedure is presented which allows for the determination of the scalar-relativistic contraction of individual electronic shells of transition metal atoms from X-ray structure factor data. The procedure is verified and benchmarked employing theoretical and experimental F(hkl) data, revealing an overall good agreement between the experimentally determined results and the theoretical reference values. From the experimental data, the relativistic contraction of the n = 2 shell of a cerium atom is, for example, determined as 0.

Topology of the electron density of d0 transition metal compounds at subatomic resolution.

Accurate X-ray diffraction experiments allow for a reconstruction of the electron density distribution of solids and molecules in a crystal. The basis for the reconstruction of the electron density is in many cases a multipolar expansion of the X-ray scattering factors in terms of spherical harmonics, a so-called multipolar model. This commonly used ansatz splits the total electron density of each pseudoatom in the crystal into (i) a spherical core, (ii) a spherical valence, and (iii) a nonspherical valence contribution.