Structural and Electronic Properties of Hydrated VnH2O and Vn+H2O, n ≤ 13, Systems

Abstract

Water adsorption on small vanadium clusters, Vn–H2O and Vn+–H2O, n ≤ 13, is crucial to understanding the details of the metal-solvation process, very difficult to determine experimentally. Therefore, by means of density functional theory, BPW91-D2 all-electron calculations with dispersion corrections, the low-lying states of Vn and Vn+ are studied in this work, where dimer motifs, acting as basic building blocks, give origin to distorted structures. The results for Vn and Vn+ are consistent with experimental determinations for ionization energies (IE), dissociation energies, and IR spectra. We found that multiple isomers are involved in the spectrum of some Vn+ ions and that the IEs are reduced by water attachment in Vn–H2O. By means of metal–oxygen bonding, V–O, water adsorption is done on atop sites of the Vn+ cations. This is confirmed by the results of vibrational analysis, which are in agreement with reported experimental findings, revealing small blue and red shifts of the bending frequency of the a...