A comprehensive investigation of the intermolecular interactions between CH₂N₂ and X₁₂Y₁₂ (x= B, Al,Ga; Y =N, P, As) nanocages

In this paper, we have theoretically determined the possibility of adsorption of the gaseous CH₂N₂ molecule on the surface of X₁₂Y₁₂ nanocages, where X = B, Al, Ga and Y = N, P, As. The electronic structure calculations have been performed by density functional theory (DFT) using four functionals (i.e., B3LYP-D3, M06-2X, ωB97XD, and CAM-B3LYP), together with the 6-311G(d) basis function. We find that the adsorption of CH₂N₂ on top of the X–Y bond of the nanocage is the most preferred site for adsorption. The adsorption process is accompanied by a charge-transfer phenomenon, which results in a strong bond between the terminal N atom of diazomethane and the X atom of the nanocage. This gives rise to significant changes in the highest and lowest occupied molecular orbital (HOMO and LUMO, respectively) energies and thus attribute properties to the nanocages that enable themto act as building blocks of CH₂N₂ sensing materials.