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Pis'ma v Zhurnal Èksperimental'noi i Teoreticheskoi Fiziki, 2023, Volume 117, Issue 5, Pages 385–386
DOI: https://doi.org/10.31857/S1234567823050105
(Mi jetpl6888)
 

This article is cited in 1 scientific paper (total in 1 paper)

CONDENSED MATTER

Formal valence, charge distribution, and chemical bond in a compound with a high oxidation state: KMnO$_4$

V. I. Anisimovab, A. R. Oganovc, M. A. Mazannikovaab, D. Y. Novoselovab, Dm. M. Korotina

a M. N. Mikheev Institute of Metal Physics of Ural Branch of Russian Academy of Sciences, 620108 Yekaterinburg, Russia
b Department of theoretical physics and applied mathematics, Ural Federal University, 620002 Yekaterinburg, Russia
c Skolkovo Institute of Science and Technology, 121205 Moscow, Russia
References:
Abstract: KMnO$_4$ 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 $\sim10$ 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 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 MnO$_4^-$ complex with negligible contribution of the ionic part.
Funding agency Grant number
Russian Science Foundation 19-12-00012
Ministry of Science and Higher Education of the Russian Federation 122021000039-4
This work was supported by the Russian Science Foundation (project no. 19-12-00012, calculations of the electronic structure) and by the Ministry of Science and Higher  Education of the Russian Federation (theme no. 122021000039-4 “Electron,” calculations of the contributions to the energy of chemical bond).
Received: 19.01.2023
Revised: 31.01.2023
Accepted: 31.01.2023
English version:
Journal of Experimental and Theoretical Physics Letters, 2023, Volume 117, Issue 5, Pages 377–383
DOI: https://doi.org/10.1134/S0021364023600143
Bibliographic databases:
Document Type: Article
Language: English
Citation: V. I. Anisimov, A. R. Oganov, M. A. Mazannikova, D. Y. Novoselov, Dm. M. Korotin, “Formal valence, charge distribution, and chemical bond in a compound with a high oxidation state: KMnO$_4$”, Pis'ma v Zh. Èksper. Teoret. Fiz., 117:5 (2023), 385–386; JETP Letters, 117:5 (2023), 377–383
Citation in format AMSBIB
\Bibitem{AniOgaMaz23}
\by V.~I.~Anisimov, A.~R.~Oganov, M.~A.~Mazannikova, D.~Y.~Novoselov, Dm.~M.~Korotin
\paper Formal valence, charge distribution, and chemical bond in a compound with a high oxidation state: KMnO$_4$
\jour Pis'ma v Zh. \`Eksper. Teoret. Fiz.
\yr 2023
\vol 117
\issue 5
\pages 385--386
\mathnet{http://mi.mathnet.ru/jetpl6888}
\crossref{https://doi.org/10.31857/S1234567823050105}
\edn{https://elibrary.ru/pybkwg}
\transl
\jour JETP Letters
\yr 2023
\vol 117
\issue 5
\pages 377--383
\crossref{https://doi.org/10.1134/S0021364023600143}
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