Doping of the first row transition metals onto B12N12 nanocage: A DFT study

A comparative study of doping of the first row transition metals (from Sc to Zn) onto all available adsorption sites of the exterior surface of B12N12 nanocage has been performed by DFT method at B3LYP/def2-TZVP(-f) level of theory. The geometrical structures, electronic properties, population and quantum theory of atoms in molecules (QTAIM) analyses are also performed to better understand the cage/metal interactions. It can be inferred from results that nine metals from Sc to Cu tend to chemisorb onto B12N12 nanocage via covalent interactions, where Zn metal physisorbed through weak Van der Waals interaction. Density of state analysis indicates that doped metal can modify significantly electronic properties of nanocage by decreasing HOMO-LUMO band gap and increasing metallic character. Besides, based on the maximum hardness and the minimum electrophilicity principles, it seems that the reactivity of the cage/metal clusters was increased compared to the pristine cage. It is also found that among the first row transition metals, Mn exhibits the strongest affinity toward B12N12 nanocage with the most negative binding energy. (C) 2018 Elsevier B.V. All rights reserved.