Abstract
Local Density calculations have been performed, using a Gaussian representation of the wave function and a model potential for the core electrons, for clusters representing a hydrogen atom diffusing through palladium and rhodium and for a CO molecule diffusing over Pd(100).
For the Pd(111) + H system, represented by a ten-atom cluster, the relative energies of the various H-atom sites are correctly given and the calculated diffusion barier (0.32eV) is in encouraging agreement with its experimental counterpart (0.23eV). For rhodium the calculated barrier is much greater (0.91eV). Calculations for rhodium at the palladium lattice spacing (about 2% greater) yield 0.71eV so that the increase relative to palladium is roughly one-third structural and two-thirds electronic.
Several cluster models, containing up to 17 atoms, have been chosen to model the atop (A), bridge (B) and 4-fold centered (C) sites for CO adsorption on Pd(100). The B site is correctly found to be the most stable, followed closely (within — 0.15eV) by C, A being significantly higher (~1.0eV). The molecule stands perpendicular to the surface at all three sites; however, along a diffusion path between B and C it tilts by as much as ~ 20°, showing a tendency for the carbon to point back towards the bridge site. The barrier for diffusion is calculated to be about 0.35eV, a reasonable value.
These “dynamic” results complement previous results on the equilibrium properties (geometries, ionization potentials, vibrational frequencies, nature of the bonding) and further help to delimit the domain of the method.
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Andzelm, J., Salahub, D. (1987). Cluster Calculations for Diffusion on and in Transition Metals. In: Jena, P., Rao, B.K., Khanna, S.N. (eds) Physics and Chemistry of Small Clusters. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-0357-3_116
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DOI: https://doi.org/10.1007/978-1-4757-0357-3_116
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