Exploring energy landscapes of charge multipoles using constrained density functional theory

DOI

We present a method to constrain local charge multipoles within density-functional theory. Such multipoles quantify the anisotropy of the local charge distribution around atomic sites and can indicate potential hidden orders. Our method allows selective control of specific multipoles, facilitating a quantitative exploration of the energetic landscape outside of local minima. Thus, it enables a clear distinction between electronically and structurally driven instabilities. We demonstrate the effectiveness of this method by applying it to charge quadrupoles in the prototypical orbitally ordered material KCuF₃. We quantify intersite multipole-multipole interactions as well as the energy-lowering related to the formation of an isolated local quadrupole. We also map out the energy as a function of the size of the local quadrupole moment around its local minimum, enabling quantification of multipole fluctuations around their equilibrium value. Finally, we study charge quadrupoles in the solid solution KCu₁₋ₓZnₓF₃ to characterize the behavior across the tetragonal-to-cubic transition. Our method provides a powerful tool for studying symmetry breaking in materials with coupled electronic and structural instabilities and potentially hidden orders.

Identifier
DOI https://doi.org/10.24435/materialscloud:sn-kd
Related Identifier https://doi.org/10.1103/PhysRevResearch.5.033172
Related Identifier https://doi.org/10.48550/arXiv.2305.13988
Related Identifier https://archive.materialscloud.org/communities/mcarchive
Related Identifier https://doi.org/10.24435/materialscloud:3w-4c
Metadata Access https://archive.materialscloud.org/oai2d?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai:materialscloud.org:1903
Provenance
Creator Schaufelberger, Luca; Merkel, Maximilian E.; Mansouri Tehrani, Aria; Spaldin, Nicola A.; Ederer, Claude
Publisher Materials Cloud
Contributor Merkel, Maximilian E.; Ederer, Claude
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 info:eu-repo/semantics/other
Format text/markdown; application/gzip
Discipline Materials Science and Engineering