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

Xia, Xinxin, Zhang, Zeng-Guang, Xu, Hong-Guang, Xu, Xiling, Kuang, Xiaoyu, Lu, Cheng, Zheng, Weijun
Journal of physical chemistry 2018 v.123 no.3 pp. 1931-1938
aluminum, density functional theory, encapsulation, nanotechnology, physical chemistry, spectroscopy
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.