Importance of intersite Hubbard interactions in β-MnO2: A first-principles DFT+U+V study

DOI

We present a first-principles investigation of the structural, electronic, and magnetic properties of pyrolusite (β-MnO2) using conventional and extended Hubbard-corrected density-functional theory (DFT+U and DFT+U+V). The onsite U and intersite V Hubbard parameters are computed using linear-response theory in the framework of density-functional perturbation theory. We show that while the inclusion of the onsite U is crucial to describe the localized nature of the Mn(3d) states, the intersite V is key to capture accurately the strong hybridization between neighboring Mn(3d) and O(2p) states. In this framework, we stabilize the simplified collinear antiferromagnetic (AFM) ordering (suggested by the Goodenough-Kanamori rule) that is commonly used as an approximation to the experimentally-observed noncollinear screw-type spiral magnetic ordering. A detailed investigation of the ferromagnetic and of other three collinear AFM spin configurations is also presented. The findings from Hubbard-corrected DFT are discussed using two kinds of Hubbard manifolds -- nonorthogonalized and orthogonalized atomic orbitals -- showing that special attention must be given to the choice of the Hubbard projectors, with orthogonalized manifolds providing more accurate results than nonorthogonalized ones within DFT+U+V. This work paves the way for future studies of complex transition-metal compounds containing strongly localized electrons in the presence of pronounced covalent interactions.

Identifier
DOI https://doi.org/10.24435/materialscloud:bf-cz
Related Identifier https://arxiv.org/abs/2106.00520
Related Identifier https://doi.org/10.1103/PhysRevMaterials.5.104402
Related Identifier https://archive.materialscloud.org/communities/mcarchive
Related Identifier https://doi.org/10.24435/materialscloud:32-xv
Metadata Access https://archive.materialscloud.org/oai2d?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai:materialscloud.org:938
Provenance
Creator Mahajan, Ruchika; Timrov, Iurii; Marzari, Nicola; Kashyap, Arti
Publisher Materials Cloud
Contributor Mahajan, Ruchika; Timrov, Iurii; Marzari, Nicola; Kashyap, Arti
Publication Year 2021
Rights info:eu-repo/semantics/openAccess; Creative Commons Attribution 4.0 International; https://creativecommons.org/licenses/by/4.0/legalcode
OpenAccess true
Contact archive(at)materialscloud.org
Representation
Language English
Resource Type info:eu-repo/semantics/other
Format text/plain; application/x-bzip2; text/markdown
Discipline Materials Science and Engineering