Quantum mechanical investigations of the thermodynamic and kinetic properties of H2-activating chemical systems with accurate first-principles wave-function and density based computational methods

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The thermodynamic and kinetic properties of H2-activating chemical systems will be investigated by accurate first-principles wave-function and density based (DFT) quantum chemical methods. The determination of H2 complexation sites, their geometries and interaction energies (including computation of van der Waals type complexes) is the initial step in all treatments. Special attention will be brought to the effects of thermal (entropic) corrections as well as the influence of solvation effects. For the interesting (reactive) cases searches for transition states, determination of the thermodynamics, computation of IR spectra, and various analysis techniques are applied. By the combination of accurate DFT-D3 gas phase and COSMORS solvation data, reliable free reaction enthalpies are computed for the first time for complex H2-activating species that can be directly compared to experimentally observed quantities. Beside methodological insight regarding the applied quantum chemical methods, the project opens the chance to develop a detailed view of hydrogen activation mechanisms and the structural factors that influence the course of the various reactions under realistic conditions. All investigations will be carried out in close collaboration with the experimental groups.