Author:
Anisimov V. I.,Oganov A. R.,Mazannikova M. A.,Novoselov D. Y.,Korotin Dm. M.
Abstract
KMnO4 has unusual formal manganese oxidation state Mn+7 that seems puzzling: the energy of creating such ion (119 eV) is much greater than the energy of chemical bonds (up to ~10 eV). We have used the Wannier functions formalism to analyze the distribution of Mn-$$3d$$ electrons and O-$$2p$$ electrons for empty electronic states in the $${\text{MnO}}_{4}^{ - }$$ complex and have found that, while formally one has $${{d}^{0}}$$ configuration for manganese ion in this compound, in reality only about one-half of the hole density described by these Wannier functions corresponding to this configuration belongs to d-electrons, while the other half is spread over surrounding oxygen atoms. This corresponds much more to Mn+7 state than to Mn+2, because the calculated total number of d‑electrons is equal to 5.25. Our analysis has also sown nearly perfect covalent type of chemical bond within the $${\text{MnO}}_{4}^{ - }$$ complex with negligible contribution of the ionic part.
Subject
Physics and Astronomy (miscellaneous)
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