Size-Dependent Structural Motifs in PtnV− (n = 2–13) cluster anions: A DFT insight

Dated: January 15, 2026) We present a density functional theory (DFT) investigation of vanadium-doped platinum cluster anions, PtnV − (n = 3–13), focusing on their size-dependent structural, energetic, and electronic properties. Global optimization using a Basin Hopping approach reveals a transition from pla-nar or quasi-planar low-symmetry structures at small sizes to compact, highly coordinated three-dimensional motifs as the Pt content increases. Energetic descriptors, including binding energies, second-order energy differences, and HOMO–LUMO gaps, identify n = 3, 5, and 10 as particularly stable cluster sizes. These enhanced stabilities arise from distinct bonding regimes, with strong Pt–V interactions dominating at small sizes and increasing Pt–Pt metallic bonding and electronic delocalization stabilizing larger clusters. A highly symmetric C3v pyramidal structure is identified as the global minimum for Pt10V − , highlighting the stabilizing role of symmetry. Bond-length and Hirshfeld charge analyses reveal nearly constant Pt–V distances and significant charge transfer from V to Pt in small clusters, followed by increased delocalization and bulk-like Pt–Pt bonding with size. Density of states calculations further confirm the crossover from molecule-like to metallic electronic behavior. Overall, these results elucidate fundamental structure–property relationships in PtnV − clusters, relevant for the rational design of V-doped platinum nanoalloys.