Structures, Spectra, and Energies of Niobium Clusters from Nb13 to Nb20

Abstract

A comprehensive theoretical investigation on structures and properties of niobium clusters in the range from 13 to 20 atoms, in three different charged states, is performed by using the BPW91 and M06 functionals and the cc-pVDZ-PP basis set. These species are predicted to prefer low spin ground state, i.e., singlet (for even electron) and doublet (for odd electron) systems. In terms of growth mechanism, a compact structure with one Nb encapsulated by a cage formed from five and six triangles is found to be favored over an icosahedral evolution. Unlike many 3d metals, whose volumes are much smaller, 13 and 19 Nb atoms clusters do not exist as icosahedra and double-icosahedra. A distinct case is Nb(15) as it bears a slightly distorted bcc structure. For some systems, several lower lying isomers are computed to be so close in energy that DFT computations cannot clearly establish their ground electronic states. The existence of structural isomers with comparable energy content is established for Nb(n) species with n = 13, 18, 19, and 20 in both neutral and charged states. The vibrational (IR) spectra are also calculated. While the spectra of smaller systems are strongly dependent on addition or removal of an electron from the neutral, the spectra of the larger size clusters are mostly independent of the charged state. The neutrals and their corresponding ions usually have a quite similar IR pattern. Electron affinities (EA), ionization energies (IE), average binding energies, dissociation energies, and frontier orbital energy gaps are evaluated. The computed EAs and IEs are generally in fair agreement with experiment. The Nb(15) system is observed to be stable and it can form a highly symmetric structure in all charged states with both open and closed electron shells.