Density functional theory studies on C₂₀ with substitutional Ti_nN_n impurities

In this paper, we have performed systematic theoretical surveys of C₂₀ and its C_20-2nTi_nN_n nanocages with n = 1-8 at DFT. Full optimization indicates none of the structures collapse to open deformed as segregated heterofullerene. Also, in order to avoid the resulted strain of fused five-pentagon configuration, some of them deform their cage at the Ti-N bonds and appear cubic-like. Binding energy (E_b) increases, and the absolute heat of atomization │ΔH_at│ of the designed C_20-2nTi_nN_n structures decreases, respectively, as the number of substituting Ti-N units increases. The calculated E_b of 57.05 eV/atom and │ΔH_at│ of 2437.40 kcal/mol display C₄Ti₈N₈ as the most thermodynamic stable heterofullerene where including eight separated Ti-N units through two double C═C bonds. In contrast, the calculated band gap of 2.06 eV shows C₁₈Ti₁N₁ as the best-insulated heterofullerene. Here isolable or extractable open-shell C₁₈Ti₁N₁ heterofullerene must be kinetic stable species, and closed-shell C₄Ti₈N₈ should be thermodynamic stable species. Compared to the suggested Ti-decorated B₃₈ fullerene as a high capacity hydrogen storage material with large E_b (5.67 eV/atom), our studied C_20-2nTi_nN_n heterofullerenes show the higher E_b with a range of 13.78 to 57.05 eV/atom, the higher stability, and the higher capacity hydrogen storage. Each Ti-N unit can bind up to two hydrogen molecules with an average adsorption energy of 0.073 eV/H₂. While the C₄Ti₈N₈ fullerene substituted with 8 Ti-N units can store 16 H₂ molecules, the hydrogen gravimetric density (the hydrogen storage capacity) reaches up to 5.61 wt% with an average adsorption energy of 0.587 eV/H₂. Based on these results, we infer that C₄Ti₈N₈ fullerene is a potential material for hydrogen storage with high capacity and might motivate active experimental efforts in designing hydrogen storage media.