Theoretical Study of Isomers of Doped Clusters L2Al42 with Transition Metal Dopants L Inside and on the Surface of the Aluminum Cage

Abstract

The structures and stabilities of internal and external isomers of nanosized L₂Al₄₂ clusters doped with transition metals L located inside and at the surface of the aluminum cage have been calculated by the density functional theory method. It has been demonstrated that, for all clusters with L = Sc-Cu, isomers with dopants in internal (closed) positions in the cluster core are preferable. Migration of dopants to surface positions to form open catalytic centers requires an energy input of ∼ 15–25 kcal/mol. Calculations predicted for the first time the possibility of existence and high stability of high-spin L₅Al₃₉ clusters with five dopants located in favorable axial and equatorial internal positions. The results can be useful for theoretical prediction and modeling of bulkier molecular aluminum alloys with a higher content of dopants L.