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  4. Pivotal Role of Intersite Hubbard Interactions in Fe-Doped alpha-MnO2
 
research article

Pivotal Role of Intersite Hubbard Interactions in Fe-Doped alpha-MnO2

Mahajan, Ruchika
•
Kashyap, Arti
•
Timrov, Iurii  
August 4, 2022
Journal Of Physical Chemistry C

We present a first-principles investigation of the structural, electronic, and magnetic properties of the pristine and Fe-doped alpha-MnO2 using density-functional theory with extended Hubbard functionals. The onsite U and intersite V Hubbard parameters are determined from first-principles and self-consistently using density-functional perturbation theory in the basis of Lowdin-orthogonalized atomic orbitals. For the pristine alpha-MnO2 we find that the so-called C2-AFM spin configuration is the most energetically favorable, in agreement with the experimentally observed antiferromagnetic ground state. For the Fe-doped alpha-MnO2 two types of doping are considered: Fe insertion in the 2 x 2 tunnels and partial substitution of Fe for Mn. We find that the interstitial doping preserves the C2 AFM spin configuration of the host lattice only when both onsite U and intersite V Hubbard corrections are included, while for the substitutional doping the onsite Hubbard U correction alone is able to preserve the C2-AFM spin configuration of the host lattice. The oxidation state of Fe is found to be +2 and +4 in the case of the interstitial and substitutional doping, respectively, while the oxidation state of Mn is +4 in both cases. This work paves the way for accurate studies of other MnO2 polymorphs and complex transition-metal compounds when the localization of 3d electrons occurs in the presence of strong covalent interactions with ligands.

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Type
research article
DOI
10.1021/acs.jpcc.2c04767
Web of Science ID

WOS:000848273000001

Author(s)
Mahajan, Ruchika
Kashyap, Arti
Timrov, Iurii  
Date Issued

2022-08-04

Publisher

AMER CHEMICAL SOC

Published in
Journal Of Physical Chemistry C
Volume

126

Issue

30

Start page

14353

End page

14365

Subjects

Chemistry, Physical

•

Nanoscience & Nanotechnology

•

Materials Science, Multidisciplinary

•

Chemistry

•

Science & Technology - Other Topics

•

Materials Science

•

density-functional theory

•

structural stability

•

manganese oxides

•

oxidation-state

•

water oxidation

•

lithium

•

mno2

•

nanorods

•

catalyst

•

chemistry

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
Available on Infoscience
September 12, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/190661
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