Probing the structural evolution and electronic properties of divalent metal BeMg clusters from small to medium-size

Bimetallic clusters have aroused increased attention because of the ability to tune their own properties by changing size, shape, and doping. In present work, a structural search of the global minimum for divalent bimetal BeMg (n = 1–20) clusters are performed by utilizing CALYPSO structural searching method with subsequent DFT optimization. We investigate the evolution of geometries, electronic properties, and nature of bonding from small to medium-sized clusters. It is found that the structural transition from hollow 3D structures to filled cage-like frameworks emerges at n = 10 for BeMg clusters, which is obviously earlier than that of Mg clusters. The Be atoms prefer the surface sites in small cluster size, then one Be atom tend to embed itself inside the magnesium motif. At the number of Mg larger than eighteen, two Be atoms have been completely encapsulated by caged magnesium frameworks. In all BeMg clusters, the partial charge transfer from Mg to Be takes place. An increase in the occupations of the Be-2p and Mg-3p orbitals reveals the increasing metallic behavior of BeMg clusters. The analysis of stability shows that the cluster stability can be enhanced by Be atoms doping and the BeMg cluster possesses robust stability across the cluster size range of n = 1–20. There is s-p hybridization between the Be and Mg atoms leading to stronger Be-Mg bonds in BeMg cluster. This finding is supported by the multi-center bonds and Mayer bond order analysis.