Photoelectron Spectroscopy and Density Functional Calculations of VGen– (n = 3–12) Clusters

Abstract

The structural, electronic and magnetic properties of VGen–/0 (n = 3–12) clusters were investigated using anion photoelectron spectroscopy in combination with density functional theory calculations. We found that the dominant geometries are exohedral for the VGen–/0 clusters with n ≤ 7. The VGe8–/0 clusters have half-encapsulated boat-shaped structures, and the opening of the boat-shaped structure is gradually covered by the additional Ge atoms to form Gen cage from n = 9–11. At n = 12, a D3d distorted hexagonal prism cage structure is formed. According to the natural population analysis, for both anionic and neutral VGen clusters of n = 8–12, there is electron transfer from the Gen framework to the V atom and the total magnetic moments decrease to the minima. The electron transfer pattern and the minimization of the magnetic moments for these clusters are related to their structural evolution.