Effects of van der Waals Interactions on the Structure and Stability of Cu8-xPdx (x=0, 4, 8) Cluster Isomers

Abstract Detailed knowledge of the minimum energy and low-lying structures of metal clusters is crucial to understand their physicochemical properties. In this work, the effect of van der Waals (vdW) interactions on the structure and stability of Cu-Pd clusters is investigated. With this aim, a global search algorithm that combines the basin-hopping method and density functional theory is used to explore the potential energy surface of Cu8-xPdx (x = 0, 4, 8) clusters. We present the structural motifs adopted by the low-energy isomers obtained with the PBE gereralized gradient exchange-correlation functional, and with PBE supplemented by dispersion energy corrections as given by Grimme’s D3 method. The isomeric structures obtained by PBE and PBE-D3 methods are in general quite similar, except for minor changes in some particular isomers. Global structural explorations were also performed with the meta-GGA TPSS and the hybrid PBE0 functionals, showing a reasonable agreement with the results obtained with the PBE and corrected PBE-D3 functionals. The energetics of the clusters is investigated by analyzing the binding energy per atom. Binding ;1;energies become larger when vdW forces are included, and this contribution increases from Cu8 to Pd8 and then to Cu4Pd4. Mixing between Cu and Pd atoms to form nanoalloys is favorable, a feature consistent with the well-known formation of intermetallic compounds in the bulk Cu-Pd alloys. The HOMO-LUMO gap indicates that some isomers in Cu8 and Cu4Pd4 are more reactive than the lowest energy isomer, a feature that gives a hint into the importance that low-lying isomers may have in catalytic reactions. Binding energies and HOMO-LUMO gaps present a stronger dependence on the exchange-correlation functional than the cluster structures.