Geometric and electronic structures of medium-sized boron clusters doped with plutonium

Abstract Doping metal heteroatoms is an effective strategy to regulate the geometric and electronic structure of boron based nanoclusters. However, the exploration of the ground state structures of metal-boron-based nanoclusters is still a challenge duo to the complexity of the bonding interactions between heterogeneous atoms and boron cluster and the number of isomers on the potential energy surface increases exponentially with cluster size. Here, we use the CALYPSO cluster structural search method in combination with density functional theory calculations to study the geometries and electronic properties of anionic boron clusters doped with plutonium (PuB n − , n = 10–20). Our results show that the medium-sized PuB 14 − cluster exhibits excellent stability with highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap of 2.30 eV. The remarkable stability of the anionic PuB 14 − cluster is due to the robust interactions between the Pu metal and the B 14 skeleton, along with the strong covalent interactions between the B atoms. These findings enrich the geometric structure database of metal doped clusters and provide valuable insights for the future synthesis of boron based nanomaterials.