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Результаты исследований: Вклад в журнал › Статья › Рецензирование
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TY - JOUR
T1 - Formal Valence, Charge Distribution, and Chemical Bond in a Compound with a High Oxidation State: KMnO4
AU - Anisimov, V. I.
AU - Oganov, A. R.
AU - Mazannikova, M. A.
AU - Novoselov, D. Y.
AU - Korotin, Dm. M.
PY - 2023/3/1
Y1 - 2023/3/1
N2 - 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 MnO4- 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. 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 MnO4- complex with negligible contribution of the ionic part.
AB - 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 MnO4- 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. 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 MnO4- complex with negligible contribution of the ionic part.
UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85149070768
UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=000942217800001
U2 - 10.1134/S0021364023600143
DO - 10.1134/S0021364023600143
M3 - Article
VL - 117
SP - 377
EP - 383
JO - JETP Letters
JF - JETP Letters
SN - 0021-3640
IS - 5
ER -
ID: 38477461