Mott gapping in 3d ABO3 perovskites without Mott-Hubbard interelectronic U

Abstract

The existence of band gaps in Mott insulators such as perovskite oxides with partially filled 3d shells has been traditionally explained in terms of strong, dynamic inter-electronic repulsion codified by the on-site repulsion energy U in the Hubbard Hamiltonian. The success of the "DFT+U approach" where an empirical on-site potential term U is added to the exchange-and correlation Density Functional Theory (DFT) raised questions on whether U in DFT+U represents interelectronic correlation in the same way as it does in the Hubbard Hamiltonian, and if empiricism in selecting U can be avoided. Here we illustrate that ab-initio DFT without any U is able to predict gapping trends and structural symmetry breaking (octahedra rotations, Jahn-Teller modes, bond disproportionation) for all ABO3 3d perovskites from titanates to nickelates in both spin-ordered and spin disordered paramagnetic phases. We describe the paramagnetic phases as a supercell where individual sites can have different local environments thereby allowing DFT to develop finite moments on different sites as long as the total cell has zero moment. We use a recently developed exchange and correlation functional ("SCAN") that is sanctioned by the usual single-determinant, mean-field DFT paradigm with static correlations, but has a more precise rendering of self-interaction cancelation. Our results suggest that strong dynamic electronic correlations are not playing a universal role in gapping of 3d ABO3 Mott insulators, and opens the way for future applications of DFT for studying a plethora of complexity effects that depend on the existence of gaps, such as doping, defects, and band alignment in ABO3 oxides.

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• $f$-electron and magnetic ordering effects in nickelates LaNiO${}_2$ and NdNiO${}_2$: remarkable role of the cuprate-like $3d_{x^2-y^2}$ band
• Origins Vs. fingerprints of the Jahn-Teller effect in d-electron ABX${}_3$ perovskites
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• Mass enhancement in 3d and s-p perovskites from symmetry breaking
• First-Principles Calculation of Spin and Orbital Contributions to Magnetically Ordered Moments in Sr${}_2$IrO${}_4$
• Untangling the structural, magnetic dipole, and charge multipolar orders in Ba${}_2$MgReO${}_6$
• First-principles study of electron and hole doping in perovskite nickelates
• Effect of the electronic charge gap on LO bond-stretching phonons in undoped La${}_2$CuO${}_4$ calculated using LDA+U
• Ab initio description of the Bi${}_2$Sr${}_2$CaCu${}_2$O${}_{8+\delta }$ electronic structure
• Critical role of magnetic moments in heavy-fermion materials: revisiting mysteries of SmB${}_6$
• Electronic and magnetic properties of perovskite selenite and tellurite compounds: CoSeO${}_3$, NiSeO${}_3$, CoTeO${}_3$ and NiTeO${}_3$
• Density Functional description of spin, lattice, and spin-lattice dynamics in antiferromagnetic and paramagnetic phases at finite temperatures
• Dependence of band gaps in d-electron perovskite oxides on magnetism
• Hidden orders in spin-orbit entangled correlated insulators
• Structural instabilities of infinite-layer nickelates from first-principles simulations
• On the calculation of the bandgap of periodic solids with MGGA functionals using the total energy
• Metal-insulator transition and local-moment collapse in negative charge-transfer CaFeO${}_3$ under pressure
• Landscape of coexisting excitonic states in the insulating single-layer cuprates and nickelates
• Charge ordering as the driving mechanism for superconductivity in rare-earth nickel oxides
• Giant Tuning of Electronic and Thermoelectric Properties by Epitaxial Strain in p-Type Sr-Doped LaCrO3 Transparent Thin Films
• Persistent half-metallic ferromagnetism in a (111)-oriented manganite superlattice
• Electron-phonon mediated superconductivity in La${}_6$Ni${}_5$O${}_{12}$ nickel oxides
• Robustness of electronic screening effects in electron spectroscopies: example of V${}_2$O${}_5$
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• Emergent half-metal with mixed structural order in (111)-oriented (LaMnO${}_3$)${}_{2n}$|(SrMnO${}_3$)${}_n$ superlattices
• A first-principles study of bcc chromium beyond the generalized gradient approximation (GGA)
• Comparison of SCAN+U and r2SCAN+U for Charge Density Wave Instability and Lattice Dynamics in CuTe
• Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor