Geometries, stabilities and electronic properties of copper and selenium doped copper clusters: Density functional theory study

Abstract The structures properties of Cu n+1 and Cu n Se clusters have been investigated using an unbiased CALYPSO structure searching method. Firstly, an unbiased search relying on several structurally different initial clusters have been undertaken. Subsequently, geometry optimization by means of density functional theory is carried out to determine the relative stability of various candidates for low lying clusters obtained from the unconstrained search. The results shown that the ground state Cu 9 cluster is found to prefer a unique and previously unrecognized structure, with the total energies much lower than all structures proposed in the literature so far. The Cu 2 Se cluster is the most stable geometries for Cu n Se clusters. Additionally, the calculated HOMO-LUMO gaps ranges from 1.27 to 2.85 eV, which make Cu n Se clusters suitable candidates in photocatalyst materials. Lastly, the molecular orbital energy and density of states; the adaptive natural density partitioning; the electron localization function, localized orbital locator and Mayer Bond order are also studied for the ground state to develop a deeper understanding on the electronic properties.