Structure stability of free copper nanoclusters: FSA-DFT Cu-building and FDM-XANES study

Highlights: • Theoretical study combined DFT + XANES simulations. • Electronic and morphological structures of Cu20 clusters. • New properties of transition metal clusters. - Abstract: We present ab initio simulations of X-ray Absorption Near-Edge Structure (XANES) spectra, performed on model clusters built by fast simulated annealing and optimized by Density Functional Theory (DFT) minimization. As is known, larger stability of Cu clusters with 20 atoms was found in comparison with those with 19 and 21 atoms. Based on this knowledge, we show the sensitivity of the XANES technique on the number of atoms n, (c.a 20), and on the morphology of the Cu_n nanoclusters. For this study we used both L3 and K edges and found the former more sensitive. In addition, in the case of the K XANES edge, we carry out the simulations using four different methods, to observe their performance in arrays of a few atoms. Even more, we obtain a good agreement between our results and previous predictions on the HOMO-LUMO gaps for these systems.