DFT insights into the sensitivity of pure and TM-doped Be12O12 nanocages (TM = Cr and Fe) toward hydrides of group V elements (XH3; X = N, P, and As)

The potency of pure and transition metal (TM)–doped Be₁₂O₁₂ nanocages (TM = Cr and Fe) toward the adsorption of XH₃ gases (X = N, P, and As) was minutely studied through different DFT computations. Upon the obtained energetic findings, the TM doping significantly escalated the efficacy of the investigated nanocage toward sensing XH₃ toxic molecules. From the energetic affirmations, the most appreciable negative adsorption and interaction energies were observed within the XH₃∙∙∙CrBe₁₁O₁₂ complexes with values up to −35.85 and −36.47 kcal/mol, respectively. The interpretations of the symmetry-adapted perturbation theory pointed out that the electrostatic force was regarded as the prevalent contribution in the adsorption process within the XH₃∙∙∙Be₁₂O₁₂ and ∙∙∙TMBe₁₁O₁₂ complexes. An extensive investigation of the noncovalent interaction index and the quantum theory of atoms in molecules analyses pinpointed the partially covalent nature of the interactions within the XH₃∙∙∙Be₁₂O₁₂ and ∙∙∙TMBe₁₁O₁₂ complexes. The observable alterations in the molecular orbitals distributions and global reactivity descriptors of the Be₁₂O₁₂ and TMBe₁₁O₁₂ nanocages after the complexation ensured the occurrence of the scouted adsorption process. In light of the calculated thermodynamic parameters, the XH₃∙∙∙TMBe₁₁O₁₂ complexes were noticed with more negative values compared to the XH₃∙∙∙Be₁₂O₁₂ ones, affirming the effect of doping in enhancing the sensitivity of the nanocage. The outcomes of this study will provide a durable ground for the experimentalists to gain a comprehensive grasp of the efficacy of the Be₁₂O₁₂ and TMBe₁₁O₁₂ nanocages in sensing toxic molecules, particularly XH₃ toxic molecules.