Charging and stabilization of Pd atoms and clusters on an electron-rich MgO surface

We report density functional theory calculations on the interaction of Pd atoms and small Pd clusters with an electron-rich MgO surface. This surface can be generated by forming a specific kind of defects, named (H+)(e−) centers, using well known chemical recipes. By deposition of gas-phase Pd atoms on the properly functionalized MgO surface, one can generate collections of small Pd cluster anions with peculiar chemical properties. The (H+)(e−) centers act as nucleation sites for diffusing Pd atoms and favor the formation of small, thermally stable Pd n - clusters. The presence of an extra charge on the metal cluster results in a large vibrational red-shift of adsorbed CO molecules. The present results intend to stimulate experimental work to produce stable metal cluster anions on the surface of an ionic oxide.