Formal Valence, Charge Distribution, and Chemical Bond in a Compound with a High Oxidation State: KMnO4
| Autor: | V. I. Anisimov, A. R. Oganov, M. A. Mazannikova, D. Y. Novoselov, Dm. M. Korotin |
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| Rok vydání: | 2023 |
| Předmět: | |
| Zdroj: | JETP Letters. 117:377-383 |
| ISSN: | 1090-6487 0021-3640 |
| DOI: | 10.1134/s0021364023600143 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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