KMnO4 has unusual formal manganese valence 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 theWannier 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 d0 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. That corresponds much more to Mn+2 state than to Mn+7, because calculated total number of d-electrons is equal to 5.25. This analysis also has shown nearly perfect covalent type of chemical bond within the \({\text{MnO}}_{4}^{ - }\) complex with negligible contribution of the ionic part.
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Anisimov, V.I., Oganov, A.R., Mazannikova, M.A. et al. Formal Valence, Charge Distribution and Chemical Bond in a Compound with a High Oxidation State: KMnO4. Jetp Lett. (2023). https://doi.org/10.1134/S0021364023600143
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DOI: https://doi.org/10.1134/S0021364023600143