The Journal of Chemical Physics, Год журнала: 2025, Номер 162(20)
Опубликована: Май 22, 2025
We present a combined photoelectron spectroscopy and multilevel computational study [B3LYP/CCSD(T)] elucidating the geometric/electronic structure aromatic stabilization of ruthenium-doped silicon clusters. Anion spectrum RuSi12− reveals two distinct detachment features at 3.34 eV [vertical energy (VDE)] 3.8–4.4 eV, with an adiabatic (ADE) 3.17 indicating significant neutral-state structural reorganization. Theoretical analysis identifies global minimum as D2d-symmetric bicapped pentagonal prism, validated by <5.5% deviation between experimental calculated VDE/ADE. RuSi12 neutral adopts D6h-symmetric hexagonal prism elongated Ru–Si bonds (2.64 vs 2.57 Å in anion), demonstrating charge-state-dependent geometric flexibility. Natural population strong charge transfer (−3.487 e on Ru while molecular orbital AdNDP/NICS analyses uncover unprecedented σ-aromaticity through 30 delocalized electrons (Hückel 4N + 2, N = 7) diatropic ring currents. Comparative studies NbSi12− highlight transition-metal-driven symmetry modulation: Ru’s 4d-orbital participation enables adaptable bonding networks (WBI: 0.44–0.48 Si–Si 0.77–0.86), contrasting Nb’s rigid σ/π-delocalized framework. This work establishes transition-metal doping strategic tool for tailoring cluster properties catalysis nanoelectronics.
Язык: Английский