Experimental electron density studies as key for understanding the chemical and physical properties in selected model systems

The topological analysis of experimentally determined electron density distributions, employing the quantum theory of atoms in molecules developed by Richard FW Bader, was used in this thesis to study chemically or physically motivated questions in appropriate model systems. First, transition metal complexes with activated C-H bonds or Si-H bonds were examined which led to a better understanding of agostic interactions. An important tool during these investigations is the so called atomic graph, which describes the characteristic spatial arrangement of the critical points of the Laplacefield of the electron density distribution in the valence shell of the relevant atoms. It reveals zones with a locally concentrated or depleted electron density distribution. This leads to the empirical rule, that a strong activation of C-H bonds or Si-H bonds is only observed when the hydrogen atom faces a pronounced charge depletion zone at the transition metal atom. In addition, the quasi one-dimensional rare-earth transition metal carbides Sc₃FeC₄, Sc₃CoC₄ and Sc₃NiC₄ were examined. Although all three compounds are isotypic at room temperature, it was revealed during this thesis, that only Sc₃CoC₄ undergoes a structural phase transition at a temperature of ∝ 70 K and becomes superconducting below a critical temperature of 4.5 K. The main reason for this behaviour is the variation of the valence electrons through the exchange of Fe by Co or Ni. This results in the occupation of progressively higher energy electronic states and a raising of the Fermi level. The change in the nature of the electronic states at the Fermi level is in turn reflected by the different atomic graphs of the transition metal atoms and the distinct physical properties of these three compounds.