DFT Analysis of Structural, Energetic and Electronic Properties of Doped, Encapsulated, and Decorated First-Row Transition Metals on B12N12 Nanocage: Part 1

The present study explores the modification of B12N12 nanocages with first-row transition metals (3d TM atoms) in the configurations: doped (TMB11N12, B12N11TM), decorated (TM@b64, TM@b66) and encapsulated (TM@B12N12) by DFT-D3 method at B3LYP/6-31G (d,p) level of theory, revealing enhanced stability and reactivity in decorated systems. Spin multiplicity analysis revealed the most stable spin state for each nanocage, showing that decorated systems are more stable at high spin. During geometry optimization, structural rearrangements were observed, with Cr@B12N12 emerging as the most stable configuration of the series, exhibiting a strong metal/cage affinity. The DOS study showed that modification with TM significantly changes the electronic properties of the nanocage, revealing a reduction in the HOMO–LUMO gap, increased reactivity and offering valuable information for applications in sensing, catalysis and energy storage. The RMSD data show that, in encapsulated systems, the TM moves from the center of mass to establish more intense interactions with the cage, as seen in the bond order analysis and it is also observed that Zn weakly interacts with B12N12 at any of the studied configurations.