Local surface structure effect on reactivity of molecules confined between metallic surfaces

Interactions between metallic surfaces separated by nanometer distances create an unusual reactivity environment. Here we evaluate the effect of the geometry given by differences in the structures of the interacting surfaces and by the presence of steps. Adsorption of an oxygen molecule and its dissociation is examined in gaps defined by interacting platinum surfaces that have separations between 5.36 and 4.70 Å, and by comparing the effect of the different gap geometries on the adsorption strength and barriers for dissociation. It is found that specific surface–surface configurations influence the electronic structure of the surface where the molecule is adsorbed, modifying the width of its d-orbital and therefore the adsorption strength due to changes in the overlap of the adsorbate molecular orbitals with the metal d-band. In addition, the degree of the molecule–metal interaction with the other surface may restrict the adsorbate mobility and its dissociation. The presence of defects may decrease the adsorbate–surface interaction strength, but the net result depends on the specific reaction and nature of the intermediates since in some cases weaker adsorptions may result in lower dissociation barriers.