Abstract
Restricted and unrestricted B3LYP/LANL2DZ and B3LYP/6-31G(d) calculations are employed to study the adsorption of benzene on small Pd7, Pd(7+3), Pt7, and Pt(7+3) clusters. Restricted calculations give the bridge-30 adsorption site as the most stable for adsorption of benzene on Pd7 cluster, while on Pd(7+3) benzene is strongly tilted, leading to an adsorption mode where two benzene π-bonds more strongly interact with the metal cluster. Unrestricted calculations (triplet spin state) strongly favor the tilted conformations so that on both Pd7 and on Pd(7+3) the tilted di-π-hcp adsorption mode is the most stable. On the Pt7 and Pt(7+3) clusters even the restricted calculations lead to the tilted di-π adsorption mode as the most stable, a result that is reinforced by the unrestricted formalism, which also favors the tilted adsorption mode. The differences between the restricted and the unrestricted calculations are much larger for platinum than for palladium, which is related to the fact that atomic palladium has closed shell electronic configuration while atomic platinum has open shell electronic configuration. The adsorption process is dominated by electron donation from the highest occupied molecular orbital of benzene to the lowest unoccupied molecular orbital of the metal clusters.
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