Ruchika Mahajan^1*, Arti Kashyap^1*, Iurii Timrov^2*

1 School of Basic Sciences, Indian Institute of Technology Mandi, Himachal Pradesh 175075, India

2 Theory and Simulation of Materials (THEOS), and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

* Corresponding authors emails: ruchika_mahajan@students.iitmandi.ac.in, arti@iitmandi.ac.in, iurii.timrov@epfl.ch

DOI10.24435/materialscloud:gs-fc [version v1]

Publication date: May 12, 2022

How to cite this record

Ruchika Mahajan, Arti Kashyap, Iurii Timrov, Electronic structure and magnetism of pristine and Fe-doped α-MnO₂ from density-functional theory with extended Hubbard functionals, Materials Cloud Archive 2022.63 (2022), doi: 10.24435/materialscloud:gs-fc.

Description

We present a first-principles investigation of the structural, electronic, and magnetic properties of the pristine and Fe-doped α-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 Löwdin-orthogonalized atomic orbitals. Among the ferromagnetic and four types of antiferromagnetic (AFM) orderings for the pristine α-MnO₂ we find the C2-AFM spin configuration to be the most energetically favorable, in agreement with the experimentally observed AFM state. The computed lattice parameters, magnetic moments, and band gaps are overall in good agreement with the experimental ones when both the onsite and intersite Hubbard corrections are included. For the Fe-doped α-MnO₂ two types of doping are considered: Fe insertion in the 2 × 2 tunnels and partial substitution of Fe for Mn. The calculated formation energies show that Fe insertion is energetically favorable, in agreement with experiments. We find that both types of doping 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 opens a door for accurate studies of other Mn oxides and complex transition-metal compounds when the localization of 3d electrons occurs in the presence of strong covalent interactions with ligands.

Materials Cloud sections using this data

Files

File name	Size	Description
README-1.txt MD5md5:e032a64e9baad43a801a7762fe426583	3.2 KiB	The README-1.txt file describes the content of the compressed file Files-1.tar.bz2
Files-1.tar.bz2 MD5md5:a28c1b574993d9647d2f07aa344dc737	301.7 MiB	Collection of all files which were used to produce the data of the paper for pristine α-MnO2 (input and output files).
README-2.txt MD5md5:bb2f6639941e21e1371458f005518e5f	3.2 KiB	The README-2.txt file describes the content of the compressed file Files-2.tar.bz2
Files-2.tar.bz2 MD5md5:d9b6cd84dc613e1352d624a679ef7bf7	632.1 MiB	Collection of all files which were used to produce the data of the paper for Fe-doped α-MnO2 (input and output files).
README-3.txt MD5md5:ca21f4c7b00081fb3b6f7763b62caa68	2.3 KiB	The README-3.txt file describes the content of the compressed file Files-3.tar.bz2
Files-3.tar.bz2 MD5md5:d07ab9a41925eb65805f9b4ea83d7f0a	3.8 MiB	Collection of all files which were used to produce the data of the paper for Bulk Mn and Fe (input and output files).

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External references

Keywords

MnO2 DFT+U DFT+U+V crystal structure density of states density-functional theory Hubbard parameters self-interactions magnetic moment band gap spin configuration Hubbard projectors orthogonalized atomic orbitals Fe-doped MnO2 oxidation state formation energy Interstitial doping substitutional doping bond length bond angles