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

我们将利用精确的第一性原理波函数和密度基量子化学方法研究氢活化化学体系的热力学和动力学性质。确定H2络合位点、它们的几何形状和相互作用能（包括计算货车范德华型络合物）是所有处理的初始步骤。将特别注意的热（熵）修正的影响，以及溶剂化效应的影响。对于有趣的（反应）的情况下搜索过渡态，确定的热力学，计算红外光谱，和各种分析技术的应用。通过准确的DFT-D3气相和COSMORS溶剂化数据的组合，可靠的自由反应的计算第一次复杂的H2-活化物种，可以直接比较实验观察到的数量。除了关于应用量子化学方法的方法论见解外，该项目还提供了一个机会，可以详细了解氢活化机制和影响现实条件下各种反应过程的结构因素。所有调查都将与实验组密切合作进行。

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.