Geometries and electronic properties of bimetallic CuVn (n=1-5) clusters and their cations: Insight from density functional calculations

The bimetallic CuVn0/+ clusters as well as bare V-n+1(0/+) (n = 1-5) clusters were studied using density functional calculations. The lowest energy geometries of CuVn0/+ (n = 1-5) along with V-n+1(0/+) clusters were identified. Comparing geometries of CuVn and Vn+1 clusters, it was found that CuVn clusters are formed by substituting a V atom with a Cu atom at the relatively lower coordination site of Vn+1 clusters. The substitution brings a slight structural change to Vn+1 clusters. The average binding energies, dissociation energies and ionization potentials were calculated for bimetallic CuVn (n = 1-5) clusters. The calculated average binding energies show that the doping Cu makes the stability of CuVn (n = 1-5) weakened as compared to Vn+1 clusters, and cationic bimetallic CuVn clusters have better stability than those of the neutrals. The Wiberg bond order, bond length and molecular orbitals all show that the multiple-bonded V-V is involved in the bimetallic CuVn (n = 1-5) clusters. (C) 2015 Elsevier B.V. All rights reserved.