PT-CATALYZED OXIDATION OF METHANE - THEORY AND EXPERIMENT()

The oxidation of methane with molecular oxygen using the atomic platin um cation as a catalyst, yielding methanol, formaldehyde, and higher o xidation products, has been studied both computationally and experimen tally. The most relevant reaction pathways have been followed in detai l. To this end a large number of stationary points, both minima and tr ansition states, have beet? optimized using a hybrid density functiona l theory method (B3LYP). At these optimized geometries, energies have been calculated using both an empirical scaling scheme (PCI-80) and th e B3LYP method employing extended basis sets with several polarization functions. Good agreement with available experimental data has been o btained. For the parts of the catalytic cycle where detailed experimen tal results have not been available, the new calculated results have c omplemented the experimental picture to reach an almost complete under standing of the reaction mechanisms. Spin-orbit effects have been inco rporated using an empirical approach, which has lead to improved agree ment with experiments. The new FTICR experiments reported in the prese nt study have helped to clarify some of the most complicated reaction sequences.