Computational roadmap of stable Mo–S nanoclusters: atomic structures and magic compositions

Nanoparticles exhibit unique properties that are harnessed in various technological fields, yet their atomic structure remains complex and challenging to determine experimentally, especially for nanoclusters. This study explores the stability and crystal structures of molybdenum-sulfur (Mo-S) nanoclusters using the evolutionary algorithm USPEX and density functional theory (DFT) calculations. We used a selection method based on "magic" clusters, whose stability is evaluated through second-order energy differences and dissociation energies. This research provides insights into the structural stability of Mo_nS_m nanoclusters, where 1 ≤ n ≤ 15, 1 ≤ m ≤ 20, highlighting compositions that are energetically favorable and resistant to decomposition. We predicted 29 stable structures of Mo-S nanoclusters, only 7 of which have previously been synthesized experimentally. Among others, we also found a metastable planar Mo₁₀S₂₀ ring, which is the smallest possible planar Mo-S nanostructure. The thermodynamic and dynamic stability of the thin film and nanotubes made of Mo₁₀S₂₀ nanoclusters were also studied in this work. These findings enhance our understanding of nanocluster chemistry and contribute to the development of advanced nanomaterials.