Photoelectron spectra of osmium and ruthenium tetroxides

Excited states of OsO4: A comprehensive time‐dependent relativistic density functional theory study

“…The PE1–5 and UV‐vis6–9 spectra of OsO 4 were well recorded, from which one sees that the primary peaks are energetically well separated from each other such that vibronic couplings can be neglected to a first approximation, unlike MnO 4 − 23. Yet, both relativistic and electron correlation effects have to be accurately accounted for.…”

“…Unfortunately, however, it is oftentimes not easy to deduce vertical transition/ionization energies from the experimental bands due to intricate vibronic structure of the spectra. The experimental assignments on the bands even differ from each other for the same system 1, 3, 5, 8, 9. On the other hand, uncertainties and discrepancies among the theoretical assignments and interpretations of the experimental bands still remain until today10, 11 and therefore request reinvestigations with more sophisticated theoretical tools.…”

“…Due to structural simplicity, high symmetry, and volatility, tetrahedral transition metal tetraoxo complexes of a formal d 0 electronic configuration have drawn a great deal of attention to spectroscopic studies. The gas phase UV‐vis excitation and photoelectron (PE) ionization spectra for such systems as OsO 4 1–9 were measured experimentally long ago. Unfortunately, however, it is oftentimes not easy to deduce vertical transition/ionization energies from the experimental bands due to intricate vibronic structure of the spectra.…”

Applied quantum chemistry

“…Since d-orbitals are easily polarizable, they readily participate in forming a wide variety of stronger and weaker bonds. These may be ordinary cr-or я-type bonds or lone pairs [749] like in O s 0 4 [399] but in most cases new types of associations are formed. These are often called coordination complexes and the discipline discussing their properties and reactions is coordination chemistry which considerably overlaps with organometallic chemistry [1425].…”

A theoretical investigation on the intermolecular potential curve between ruthenium tetroxide and NOX (X = 1, 2)

“…Namely, the interaction involves both the bond formation between the nitrogen atom and oxo ligand and electron transfer from NO X radical to RuO 4 until the NO X adduct is yielded. The direction of electron transfer is readily predicted by ionization energies of gaseous RuO 4 (12.09–12.33 eV) [26–31], NO (9.23–9.26 eV) [32–38], and NO 2 (9.59–10.4 eV) [39–41]. As shown later, the small difference of NO and NO 2 ionization energies appears on the PECs.…”