Effects Of Manganese Doping On The Structures And Electronic Properties Of Small-sized Boron Clusters

Cluster is a kind of relatively stable matter linked by different physical or chemi-cal interactions,which consists of several or more than thousands of atoms,molecules or ions.It is a new level of physical structure between individual atoms or molecules and macroscopic solids.And it has a series of special physical or chemical proper-ties,which vary with the number of atoms contained in clusters.Atomic doping of clusters is known as an effective approach to stabilize or modify the structures and properties of clusters.And metal doping can significantly enrich the structures of boron clusters.Some peculiar geometries can be formed when appropriate metal atoms are incorporated.Different metal atoms have different effects on modifying the structures of B clusters through both geometric and electronic factors.We herein report the effect of manganese?Mn?doping on the structure evolution of small-sized boron?B?clusters.The global minimum structures of both neutral and charged Mn doped B cluster MnB_n^Q?n=10-20 and Q=0,? 1?have been proposed through extensive first-principles swaxm-intelligence based structure searches.It is found that Mn doping has significantly modified the grow behaviors of B cluster-s,leading to two structural transitions of B structure from planar to tubular and then to cage-like structures in both neutral and charged species.Half-sandwich-type structures are most favorable for small MnB_n^-/0/+?n?13?clusters and gradu-ally transform to Mn-centered double-ring tubular structures at MnB16^-/0/+ clusters with superior thermodynamic stabilities compared with their neighbors.Endohe-dral cages become the ground-state structures for larger MnB_n^-/0/+?n>19?clusters,among which MnB²⁰⁺ adopts a highly symmetric structure with superior thermody-namic stability and a large HOMO-LUMO gap of 4.53 eV.The stability of the en-dohedral MnB²⁰⁺ cage is attributed to the geometric fit and formation of 18-electron closed-shell configuration.