Getting the manifold right: The crucial role of orbital resolution in DFT+U for mixed d-f electron compounds

Abstract

Accurately modeling compounds with partially filled $d$ and $f$ shells remains a hard challenge for density-functional theory, due to large self-interaction errors stemming from local or semi-local exchange-correlation functionals. Hubbard $U$ corrections can mitigate such errors, but are often detrimental to the description of hybridized states, leading to spurious force contributions and wrong lattice structures. Here, we show that careful disentanglement of localized and delocalized states leads to accurate predictions of electronic states and structural distortions in ternary monouranates (AUO${}_4$, where A represents Mn, Co, or Ni), for which standard $U$ corrections generally fail. Crucial to achieving such accuracy is a minimization of the mismatch between the spatial extension of the projector functions and the true coordination geometry. This requires Wannier-like alternatives to atomic-orbital projector functions, or corrections of Hubbard manifolds exclusively comprised of the most localized A-$3d$, U-$5f$ and O-$2p$ orbitals. These findings open up the computational prediction of fundamental properties of actinide solids of critical technological importance.

References in corpus (32)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Advanced capabilities for materials modelling with Quantum ESPRESSO
• A linear response approach to the calculation of the effective interaction parameters in the LDA+U method
• Quantum ESPRESSO toward the exascale
• Hubbard-corrected DFT energy functionals: the LDA+U description of correlated systems
• Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
• Hubbard parameters from density-functional perturbation theory
• Hubbard U and Hund's Exchange J in Transition Metal Oxides: Screening vs. Localization Trends from Constrained Random Phase Approximation
• Self-consistent Hubbard parameters from density-functional perturbation theory in the ultrasoft and projector-augmented wave formulations
• Extended DFT+U+V method with on-site and inter-site electronic interactions
• First principles study of electronic and structural properties of CuO
• The role of spin in the calculation of Hubbard $U$ and Hund's $J$ parameters from first principles
• Energetics and cathode voltages of LiMPO${}_4$ olivines (M = Fe, Mn) from extended Hubbard functionals
• Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost
• Subspace representations in ab initio methods for strongly correlated systems
• First-principles Hubbard U and Hund's J corrected approximate density-functional theory predicts an accurate fundamental gap in rutile and anatase TiO2
• Pulay forces in density-functional theory with extended Hubbard functionals: From nonorthogonalized to orthogonalized manifolds
• Obtaining correct orbital ground states in $f$ electron systems using a nonspherical self-interaction corrected LDA+$U$ method
• Trends in the valence band electronic structures of mixed uranium oxides
• Orbital-resolved DFT+U for molecules and solids
• Importance of intersite Hubbard interactions in $\beta$-MnO${}_2$: A first-principles DFT+$U$+$V$ study
• Projectability disentanglement for accurate and automated electronic-structure Hamiltonians
• A DFT+U type functional derived to explicitly address the flat plane condition
• Understanding the role of Hubbard corrections in the rhombohedral phase of BaTiO${}_3$
• Explicit demonstration of the equivalence between DFT+U and the Hartree-Fock limit of DFT+DMFT
• Importance of ligand on-site interactions for the description of Mott-insulators in DFT+DMFT
• Automated mixing of maximally localized Wannier functions into target manifolds
• First-principles Hubbard parameters with automated and reproducible workflows
• Delocalized polaron and Burstein-Moss shift induced by Li in $\alpha$-${\text{V}}_2{\text{O}}_5$: DFT+DMFT study
• Anomalous Reversal of Stability in Mo-containing Oxides: A Difficult Case Exhibiting Sensitivity to DFT+U and Distortion

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