Geometric Structures and Electronic Properties of AlnV0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Aluminum and aluminum-doped clusters have gained much attention in cluster science due to their potential applications in nanotechnology. Here, we report a combined photoelectron spectroscopy and density functional theory study of V-doped aluminum clusters. The lowest-energy geometric structures of neutral and anionic AlnV0/– (n = 5–14) clusters are identified by comparing the theoretical photoelectron spectra with the experimental results. Our results reveal that ground-state structural evolution of neutral and anionic clusters follows different patterns. The V atom in neutral AlnV clusters moves from convex capped to surface-substituted, to encapsulated site at n = 12, and then returns to surface-substituted sites again. However, as for the anionic AlnV–, the metal V atom always occupies the convex capped sites with the cluster size increasing to n = 14. The most stable structure of Al14V– cluster possesses a C3v symmetric cagelike structure with the highest occupied molecular orbital–lowest unoccupied molecular orbital gap of 1.52 eV. Molecular orbital and adaptive natural density partitioning analysis of Al14V– suggests that the peripheral Al–Al interactions and delocalized Al–V interactions play important roles in its structural stability.