Polarization of ionic and electronic defects in response to high electric fields plays an essential role in determining properties of materials in applications such as memristive devices. However, isolating the polarization response of individual defects has been challenging for both models and measurements. Here the authors quantify the nonlinear dielectric response of neutral oxygen vacancies, comprised of strongly localized electrons at an oxygen vacancy site, in perovskite oxides of the form
The density-functional theory is widely used to predict the physical properties of materials. However, it usually fails for strongly correlated materials. A popular solution is to use the Hubbard correction to treat strongly correlated electronic states. Unfortunately, the values of the Hubbard
- Award ID(s):
- 1726534
- NSF-PAR ID:
- 10305089
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- npj Computational Materials
- Volume:
- 7
- Issue:
- 1
- ISSN:
- 2057-3960
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract AB O3. Their approach implements a computationally efficient local HubbardU correction in density functional theory simulations. These calculations indicate that the electric dipole moment of this defect is correlated positively with the lattice volume, which they varied by elastic strain and by A‐site cation species. In addition, the dipole of the neutral oxygen vacancy under electric field increases with increasing reducibility of the B‐site cation. The predicted relationship among point defect polarization, mechanical strain, and transition metal chemistry provides insights for the properties of memristive materials and devices under high electric fields. -
null (Ed.)Accurate computational predictions of band gaps are of practical importance to the modeling and development of semiconductor technologies, such as (opto)electronic devices and photoelectrochemical cells. Among available electronic-structure methods, density-functional theory (DFT) with the Hubbard U correction (DFT+U) applied to band edge states is a computationally tractable approach to improve the accuracy of band gap predictions beyond that of DFT calculations based on (semi)local functionals. At variance with DFT approximations, which are not intended to describe optical band gaps and other excited-state properties, DFT+U can be interpreted as an approximate spectral-potential method when U is determined by imposing the piecewise linearity of the total energy with respect to electronic occupations in the Hubbard manifold (thus removing self-interaction errors in this subspace), thereby providing a (heuristic) justification for using DFT+U to predict band gaps. However, it is still frequent in the literature to determine the Hubbard U parameters semiempirically by tuning their values to reproduce experimental band gaps, which ultimately alters the description of other total-energy characteristics. Here, we present an extensive assessment of DFT+U band gaps computed using self-consistent ab initio U parameters obtained from density-functional perturbation theory to impose the aforementioned piecewise linearity of the total energy. The study is carried out on 20 compounds containing transition-metal or p-block (group III-IV) elements, including oxides, nitrides, sulfides, oxynitrides, and oxysulfides. By comparing DFT+U results obtained using nonorthogonalized and orthogonalized atomic orbitals as Hubbard projectors, we find that the predicted band gaps are extremely sensitive to the type of projector functions and that the orthogonalized projectors give the most accurate band gaps, in satisfactory agreement with experimental data. This work demonstrates that DFT+U may serve as a useful method for high-throughput workflows that require reliable band gap predictions at moderate computational cost.more » « less
-
more » « less
Realistic description of competing phases in complex quantum materials has proven extremely challenging. For example, much of the existing density-functional-theory-based first-principles framework fails in the cuprate superconductors. Various many-body approaches involve generic model Hamiltonians and do not account for the interplay between the spin, charge, and lattice degrees of freedom. Here, by deploying the recently constructed strongly constrained and appropriately normed (SCAN) density functional, we show how the landscape of competing stripe and magnetic phases can be addressed on a first-principles basis both in the parent insulator YBa2Cu3O6and the near-optimally doped YBa2Cu3O7as archetype cuprate compounds. In YBa2Cu3O7, we find many stripe phases that are nearly degenerate with the ground state and may give rise to the pseudogap state from which the high-temperature superconducting state emerges. We invoke no free parameters such as the Hubbard
U , which has been the basis of much of the existing cuprate literature. Lattice degrees of freedom are found to be crucially important in stabilizing the various phases. -
more » « less
Abstract Within density functional theory (DFT), adding a Hubbard
U correction can mitigate some of the deficiencies of local and semi-local exchange-correlation functionals, while maintaining computational efficiency. However, the accuracy of DFT+U largely depends on the chosen HubbardU values. We propose an approach to determining the optimalU parameters for a given material by machine learning. The Bayesian optimization (BO) algorithm is used with an objective function formulated to reproduce the band structures produced by more accurate hybrid functionals. This approach is demonstrated for transition metal oxides, europium chalcogenides, and narrow-gap semiconductors. The band structures obtained using the BOU values are in agreement with hybrid functional results. Additionally, comparison to the linear response (LR) approach to determining U demonstrates that the BO method is superior. -
more » « less
We gauge the importance of self-interaction errors in density functional approximations (DFAs) for the case of water clusters. To this end, we used the Fermi–Löwdin orbital self-interaction correction method (FLOSIC) to calculate the binding energy of clusters of up to eight water molecules. Three representative DFAs of the local, generalized gradient, and metageneralized gradient families [i.e., local density approximation (LDA), Perdew–Burke–Ernzerhof (PBE), and strongly constrained and appropriately normed (SCAN)] were used. We find that the overbinding of the water clusters in these approximations is not a density-driven error. We show that, while removing self-interaction error does not alter the energetic ordering of the different water isomers with respect to the uncorrected DFAs, the resulting binding energies are corrected toward accurate reference values from higher-level calculations. In particular, self-interaction–corrected SCAN not only retains the correct energetic ordering for water hexamers but also reduces the mean error in the hexamer binding energies to less than 14 meV/
from about 42 meV/ for SCAN. By decomposing the total binding energy into many-body components, we find that large errors in the two-body interaction in SCAN are significantly reduced by self-interaction corrections. Higher-order many-body errors are small in both SCAN and self-interaction–corrected SCAN. These results indicate that orbital-by-orbital removal of self-interaction combined with a proper DFA can lead to improved descriptions of water complexes.
