Theoretical studies of structural, electronic, and magnetic properties for small V 2 F n 0,− (2 ≤ n ≤ 7) clusters using first-principles calculations

The structural, electronic, and magnetic properties of V 2 F n 0,− (2 ≤ n ≤ 7) clusters are investigated by using density functional theory (DFT) calculations. The spin multiplicities of the lowest isomers of the optimized V 2 F n 0,− (2 ≤ n ≤ 7) clusters are generally high, and V 2 F 6 exhibits the highest stability. The largest electron affinity (≈ 4.976 eV) of V 2 F 7 among the systems may reflect superhalogen nature of this cluster. The polarizability analysis reveals that V 2 F 2 − or V 2 F 5 − cluster has the largest or smallest polarizability anisotropy invariant, corresponding to the strongest or weakest anisotropic response to the external field, respectively. The total magnetic moments of mixed V 2 F n 0,− clusters are in the range of 3–7 μ B , mainly arising from the local magnetic moments of V atoms with unfilled 3d shell. The atoms at the symmetrical positions of the clusters have the same magnetic moments. As for the calculated IR and Raman spectra, the larger number n of F atoms of the clusters is associated with the more vibration peaks, with the highest peaks largely attributable to the stretching vibrations of F atoms.