Prediction of Structures and Atomization Energies of Coinage Metals, (M)n, n < 20: Extrapolation of Normalized Clustering Energies to Predict the Cohesive Energy.

Abstract

The geometries of the group 11 coinage metals (n = 2-20) were optimized to determine the lowest energy isomers for each cluster size, singlets for even numbers and doublets for odd numbers. For copper and silver, 2-D (planar) geometries were favored up to n = 6. For gold, 2D (planar) geometries were favored up to n = 13. Normalized clustering energies were plotted as a function of cluster size (n-1/3, for n = 4-20) with various DFT functionals and the CCSD(T)-F12b method and were extrapolated to predict the bulk cohesive energy. In the case of copper and silver, there is excellent agreement between the cohesive energies predicted at the CCSD(T)-F12b level of theory and the experimental values. For gold, the CCSD(T)-F12b values needed to be corrected for spin-orbit relativistic effects to obtain good agreement with experiment. Electronic properties including the HOMO-LUMO gaps for the even clusters and the spin densities for the odd clusters were calculated. The lowest gap is predicted to occur for n = 16 where the HOMO and LUMO are very similar in shape.