Structures and Electronic Properties of V3Sin- (n=3-14) Clusters: A Combined Ab Initio and Experimental Study

Vanadium-doped silicon cluster anions, V3Sin- (n = 3-14), have been generated by laser vaporization and investigated by anion photoelectron spectroscopy. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) Of these clusters were obtained. Meanwhile, genetic algorithm (GA) combined with density functional theory (DFT) calculations are employed to determine their groundstate structures systematically. Excellent agreement is found between theory and experiment. Among the V3Sin- clusters, V3Si5-, V3Si9-, and V3Si12- are relatively more stable. Generally speaking, three V atoms prefer to stay close with others and form strong V-V bonds. Starting from V3Si11-, cage configurations with one interior V atom emerge.