Theoretical investigation of photoelectron spectra and magnetically induced current densities in ring-shaped transition-metal oxides

Abstract

The molecular structures of cyclic group 6 transition-metal (M = Cr, Mo, W, Sg) oxides (M3O90/1−/2−) species have been optimized at density functional theory (DFT) levels. The photoelectron spectra (PES) of M3O9− (M = Cr, Mo, W) were calculated at the time-dependent DFT and approximate coupled-cluster singles doubles (CC2) levels and compared with experimental results. The CC2 calculations did not yield any reliable PES, whereas the molecular structures can be identified by comparing PES obtained at the DFT level with experiment. Magnetically induced current densities were calculated at the DFT level using the gauge-including magnetically induced current (gimic) approach. The current strengths and current pathways of the neutral M3O9 and the dianionic M3O92− (M = Cr, Mo) oxides were investigated and analyzed with respect to a previous prediction of d-orbital aromaticity for Mo3O9 anions. Current-density calculations provide ring-current strengths that are used to assess the degree of aromaticity. Comparison of current-density calculations and calculations of nucleus-independent chemical shifts (NICS) shows that NICS calculations are not a reliable tool for determining the degree of aromaticity of the metal oxides.