Anion photoelectron spectroscopy and density functional theory study of TM2Sin− (TM = V, Cr; n = 14–20) clusters

Abstract

We investigated the structural evolution and electronic properties of medium-sized silicon cluster anions doped with two transition metal atoms, TM₂Si_n⁻ (TM = V, Cr; n = 14–20), by using mass-selective anion photoelectron spectroscopy combined with density functional theory (DFT) calculations. Putative ground state structures of these clusters were obtained by using a genetic algorithm coupled with the DFT calculations. It was found that the two TM atoms tend to form a TM–TM bond, which – except for V₂Si₁₉⁻ – is shorter than the nearest neighbour distance in the crystalline state of the respective metals. The V₂Si_n⁻ clusters with n = 14 to 17 exhibit structures based on a silicon hexagonal antiprism, while the larger ones exhibit more fullerene-like cage structures. Cr₂Si_n⁻ clusters follow the same trend, although with a silicon hexagonal prism structure for n = 14 and 15, and the transition to fullerene-like structures occurring at n = 17. Among these clusters, TM₂Si₁₈⁻ have the largest average binding energy and second order differences in energy, therefore the highest relative stability. All of the clusters possess total magnetic moment of 1 μB, but with very different contributions from the doped TM atoms. Especially in the Cr doped clusters there is a tendency towards an anitiferromagnetic arrangement of the magnetic moments of the two Cr atoms.