Pd deposits on Ni(111): a theoretical study

The ASED-MO method has been used to gather electronic and energetic information on Pd deposits on Ni(111) and Pd atom inclusion in the first Ni layer since these model catalysts exhibit a striking catalytic efficiency towards butadiene hydrogenation. The electronic structure of Pd atoms is strongly altered compared with pure Pd. A Pd(4d)→Pd(5s) electronic transfer occurs in the case of the deposit when a slight similar transfer and a charge transfer from Pd to surrounding Ni takes place in the case of the inclusion. Those results are consistent with XPS experimental data. A low density of states, near the Fermi level, is also observed. The optimal geometrical situation for Pd deposits is found to be 2D-aggregates (in pseudoepitaxy or pseudomorphy with the underlying Ni surface, depending on the aggregate size). Small aggregates (part of the first Ni layer) are found to be the most stable in the case of a Pd inclusion in the Ni with a Pd---Pd distance of 2.64 Å, in agreement with available EXAFS experimental data.