Density Functional Study of the Structure and Properties of Cu₉ and Cu₉^-

Abstract

This work presents a study of the structure of neutral and anionic copper cluster nonamers with density functional theory calculations. The structure optimization and frequency analysis were performed at the local density approximation (LDA) level of theory with the exchange correlation functional by Vosko, Wilk, and Nusair (VWN). Improved calculations for the structure stability were based on the generalized gradient approximation (GGA) where the exchange correlation functional of Perdew and Wang (PW) was used. For both neutral and anionic clusters, new isomers are found that are more stable than those already presented in the literature. Adiabatic and vertical electron affinities are calculated and compared with the experimental value reported for Cu9. The calculated values are in good agreement with the available experimental data. An analysis of the most relevant molecular orbitals (MOs) of the low-lying neutral and anionic copper cluster nonamers is reported, too.

Comparative density functional theory studies of Cu clusters

“…There has been much discussion about the cluster size for the planar to 3-D transition for Cu. 22,32,34 We found that copper clusters are more stable in the planar structure of clusters with n≤6, in agreement with the previous experimental 20 and theoretical results. 15,21,34,42 Table 1 and Table 4 list the theoretical and experimental values for the bond length and binding energy for the Cu dimer.…”

Theoretical Investigation of Adsorption of Molecular Oxygen on Small Copper Clusters

“…As has been pointed out in earlier investigations, in considering adsorbate addition one has to consider not only the most stable structures of the clusters, but also their other low-energy isomers, as the adsorption energetics of the latter may be competitive with or even exceed that of the most stable conformations. Earlier, DFT-based calculations − identified a number of stable isomeric forms of copper clusters. In a series of recent studies ,, we continued to explore the structures and electronic properties of small and intermediate size neutral and anionic Cu N .…”

“…Here we report results of a computational study of molecular adsorption of O 2 on small Cu N , N = 2–10, clusters. Copper clusters have been the subject of many experimental − and theoretical − investigations. Studies − based on density functional theory (DFT) calculations revealed that copper clusters adopt planar structures for N ≤ 6, three-dimensional layered morphologies for N ≤ 16, and icosahedron-based compact structures for larger sizes in their lowest energy conformations.…”

Density functional theory for transition metals and transition metal chemistry

“…Calaminici et al 893 employed the same density functionals as Rolda´n et al but focused in detail on neutral and anionic Cu 9 . The work was motivated by significant disagreement between prior theoretical studies 894 and experiment 895 for the electron affinity of the nonameric cluster.…”