No abstract

The topological analysis of the electron localization function (ELF) provides a convenient theoretical framework to characterize chemical bonds. This method does not rely on the particular approximations that are made in actual quantum chemical calculations of the electronic structure. In principle, it can be applied to exact wave functions as well as to experimental electron densities. Introduction of a control space, such as a set of reaction pathways, allows extension of the analysis to chemical reactions. The study of the bifurcations occurring during such processes is of particular interest for their classification and their qualitative description. This is achieved with the help of René Thom's catastrophe theory. The following examples are discussed:  the ammonia inversion, the breaking of the ethane C−C bond, and the breaking of the dative bond in NH3BH3. The types of catastrophe and their unfolding have been determined for each of these processes. As by-products, nonempirical definitions of covalent and dative bonds are proposed.

The topotactic transformation of boehmite (AlOOH) taking place under calcination and leading to γ-alumina (γ-Al2O3) has been investigated theoretically and a step-by-step mechanism for the structural transformation is proposed. This mechanism reveals two major steps. First, the structural collapse of boehmite occurs, after hydrogen transfers and water extraction. Then, through an aluminum migration process, the γ-alumina characteristics appear. The proposed mechanism demonstrates the existence of an equilibrium structure for γ-alumina containing 25−31% of tetrahedral aluminum sites in agreement with nuclear magnetic resonance (NMR) results. Temperature effects on the thermodynamic stability of the different structures involved in the mechanism has been investigated. Theoretically simulated X-ray diffraction (XRD) patterns confirm the validity of our model structures. According to this mechanism, a coherent skeleton of γ-alumina inherited from the original AlOOH network is constructed. This skeleton can be regarded as a primary matrix providing an insight into structural properties of γ-alumina. Finally, the structures involved in this process may constitute a basis for further investigation on the series of metastable alumina phases appearing before the final conversion of AlOOH to α-alumina (α-Al2O3).