Structure of V-doped Pdn (n = 2–12) clusters and their ability for H2 dissociation

Abstract The structure and stability of V-doped Pd n ( n  = 2–12) clusters as well as their ability for hydrogen dissociation are analyzed using a successive growth algorithm coupled with density functional theory (DFT) computations. From the structural point of view, the lowest energy structures of these clusters are three-dimensional with exohedral geometries for n  = 2–7 whereas endohedral for n = 8 onward. From their second-order energy differences, Pd 4 V and Pd 10 V are found to be the most stable ones. Among the Pd n V(H 2 ) complexes, Pd 6 V 2H possesses the highest stability, as it is supported by the chemisorption energy, the vertical ionization potential ( VIP ), and the vertical electron affinity ( VEA ), respectively. Most importantly, the hydrogen dissociation pathway on Pd n V clusters with n  = 3, 4 and 10–12 shows that these clusters are rigid and suitable to dissociate H 2 while for n  = 5–9 the structure of the clusters changes. The H 2 dissociation process on Pd n V clusters with n = 8, 10, and 11 carries out barrierless.