Fundamental understanding of molecular reactions on metal surfaces is important for improving heterogeneous catalysis. Therefore, the reaction of small molecules on well-defined metal surfaces is... Show moreFundamental understanding of molecular reactions on metal surfaces is important for improving heterogeneous catalysis. Therefore, the reaction of small molecules on well-defined metal surfaces is investigated with state-of-the-art DFT calculations. Efforts are made to improve the agreement between experiment and theory by employing density functionals belonging to a higher level of theory than typically used. Furthermore, molecular dynamics are performed both with ab initio calculations and precomputed potential energy surfaces to investigate reaction mechanisms. This way dynamical aspects of reaction mechanisms can be investigated, e.g., the effect of rovibrational excitation of a molecule on the reaction probability and mechanism. Show less
Metals surfaces form a group of effective catalysts for the reaction of small molecules such as hydrogen (H2). In order to improve the predictive power of theory with respect to the catalytic... Show moreMetals surfaces form a group of effective catalysts for the reaction of small molecules such as hydrogen (H2). In order to improve the predictive power of theory with respect to the catalytic activity of small molecules reacting at metal surfaces, the way in which metal surfaces modify the potential energy of molecules needs to be understood at a fundamental level. Currently density functional theory (DFT) is the only electronic structure method that is accurate enough to achieve chemical accuracy while being cheap enough to make large comparative studies feasible. The work in this thesis is concerned with the creation of highly accurate density functionals that can give a simultaneously good description of the metal surface, the molecule, and the molecule interacting with the metal surface, as well as the description and simulation of supersonic molecular beam experiments and associative desorption experiments needed to validate the obtained results. Show less
This research was about to better understanding of heterogeneous catalyzed processes which would help to design better and more efficient catalysts but it is hard to achieve because of their high... Show moreThis research was about to better understanding of heterogeneous catalyzed processes which would help to design better and more efficient catalysts but it is hard to achieve because of their high level of complexity. In this way, we compared molecular beam experiments with molecular dynamics simulations to improve over the theoretical method used, called density functional theory (DFT), to achieve chemical accuracy (i.e., errors smaller than 1 kcal/mol) for the reaction studied. Show less
