Аннотация:
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.
Electronic structure calculations were performed with the support of the Russian Science Foundation
(project # 19-12-00012), contributions to the energy of chemical bond are obtained within the state assignment
of Ministry of Science and Higher Education of the Russian Federation (theme “Electron” # 122021000039-4).
Поступила в редакцию: 19.01.2023 Исправленный вариант: 31.01.2023 Принята в печать: 31.01.2023
Образец цитирования:
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$_4$”, Письма в ЖЭТФ, 117:5 (2023), 385–386; JETP Letters, 117:5 (2023), 377–383
\RBibitem{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 Письма в ЖЭТФ
\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}
Образцы ссылок на эту страницу:
https://www.mathnet.ru/rus/jetpl6888
https://www.mathnet.ru/rus/jetpl/v117/i5/p385
Эта публикация цитируется в следующих 1 статьяx:
Vladimir I. Anisimov, Artem R. Oganov, Dmitry M. Korotin, Dmitry Y. Novoselov, Alexey O. Shorikov, Alexander S. Belozerov, The Journal of Chemical Physics, 160:14 (2024)