Quantum Chemical Modelling Case Studies Relevant to Metal Oxide Dissolution and Catalysis

Over the past 20 years quantum-chemical methods have been developed sufficiently so that they can now be applied to the elucidation of the complex mechanistic processes that occur during metal oxide dissolution and catalysis reactions. Many of the reactions occurring during these processes are not directly accessible to experimental techniques and therefore quantum-chemical modelling can be applied to probe the individual reaction steps involved in the overall mechanism. Quantum chemistry provides the means of calculating the electronic properties of solids (e. g. band structures) structural properties of solids and surfaces (for instance surface relaxation and rumpling) heats of formation and reaction, activation energies, spectroscopic excitation energies and vibrational frequencies. Three case studies are described, which have been chosen to cover a range of quantum chemical applications and methodologies. These case studies are a) the dissolution mechanism of MgO, b) the parameterisation of titanium dioxide for the determination of electronic properties and c) the mechanism and energetics of adsorption of Pd onto rutile. These case studies utilise Hartree-Fock semiempirical and ab initio quantum-chemical methods as well as density functional methodologies. A range of model types are used, namely cluster models embedded in pseudo-atoms, 3-dimensional periodic models and 2-dimensional periodic surface models.