Hubbard U through polaronic defect states

Since the preliminary work of Anisimov and co-workers, the Hubbard corrected DFT+U functional has been used for predicting properties of correlated materials by applying on-site effective Coulomb interactions to specific orbitals. However, the determination of the Hubbard U parameter has remained under intense discussion despite the multitude of approaches proposed. Here, we define a selection criterion based on the use of polaronic defect states for the enforcement of the piecewise linearity of the total energy upon electron occupation. A good agreement with results from piecewise-linear hybrid functionals is found for the electronic and structural properties of polarons, including the formation energies. The values of U determined in this way are found to give a robust description of the polaron energetics upon variation of the considered state. In particular, we also address a polaron hopping pathway, finding that the determined value of U leads to accurate energetics without requiring a configurational-dependent U. It is emphasized that the selection of U should be based on physical properties directly associated with the orbitals to which U is applied, rather than on more global properties such as band gaps and band widths. For comparison, we also determine U through a well-established linear-response scheme finding noticeably different values of U and consequently different formation energies. Possible origins of these discrepancies are discussed. As case studies, we consider the self-trapped electron in BiVO₄, the self-trapped hole in MgO, the Li-trapped hole in MgO, and the Al-trapped hole in 𝛼-SiO₂.

Identifier
Source https://archive.materialscloud.org/record/2023.4
Metadata Access https://archive.materialscloud.org/xml?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai:materialscloud.org:1587
Provenance
Creator Falletta, Stefano; Pasquarello, Alfredo
Publisher Materials Cloud
Publication Year 2023
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 Dataset
Discipline Materials Science and Engineering