A density functional study on equilibrium geometries, stabilities and electronic properties of Au5Li binary clusters

Abstract

All electron scalar relativistic calculations have been performed to investigate the electronic structures of isomeric Au5Li binary clusters at the BLYP/DNP level of theory. The properties of these clusters are compared with the pristine Au6 clusters. As in case of the pure Au6 cluster, the minimum energy structure of the bimetallic Au5Li cluster is triangular with the lithium atom at the mid position. It is found that substitution of a gold atom by a lithium atom in the Au6 clusters leads to an increase in the binding energy per atom, the HOMO–LUMO gap and the chemical hardness of the structures. Thus, lithium substitution leads to stabilization of the Au6 clusters. Further, the response of various sites of the minimum-energy triangular Au5Li and Au6 clusters towards impending electrophilic and nucleophilic attacks has been determined using DFT-based local reactivity descriptors. It is found that lithium substitution leads to an increase in the number of sites prone to attack by nucleophiles like CO or H2O.