Density Functional Theory Studies on the Structures and No Molecule Adsorption and Dissociation of Rhmpdn (M + N = 13) Clusters

Abstract

Density functional theory (DFT) is used to systematically study the geometric structures, stability, electronic properties, NO molecule adsorption and dissociation properties of the mixed RhmPdn (m + n = 13) clusters.   Rh1Pd12 has Ih symmetry, the lowest mixing energy Emix, the highest second-order energy difference Δ2E, electronegativity χ and the average bond length as well as moderate average charge transfer of Rh atoms.   NO molecule tends to be adsorbed on Rh1Pd12 by means of end-on with its N atom connecting to metal atoms of the cluster, preferably at the hollow site to the top or bridge site.    For the dissociation of NO as a key step in its reduction, although the dissociation of NO into O and N atoms has a high dissociation energy barrier, complete dissociation of NO molecule actually needs only little energy (≈ 0.28 eV) owing to the released energy during adsorption.

Keywords: Icosahedral RhmPdn clusters, Density functional Theory (DFT), Structural stability, Electronic properties, NO dissociation