Interaction of Mo(CO) 6 and its derivative fragments with the Cu(001) surface: Influence on the decomposition process

International audienceA theoretical study on the adsorption and decomposition of molybdenum carbonyl on the copper (001) surface is reported. The adsorption structures and energies of Mo(CO) n molecules (n=1.. . 6) are computed systematically using Density Functional Theory (DFT) with Van der Waals corrections. By analyzing the energies of the various conformations, the main factors that determine the stable adsorption geometry are identified. Insight into the thermodynamics of decomposition is gained by calculating the reaction energy for dissociation of Mo(CO) n into Mo(CO) n−1 and CO. In the gas phase, this reaction is highly endothermic for all n. On the Cu surface however, removal of the first CO group (n=6) becomes strongly exothermic. The subsequent dissociation steps (n