Comparison of approximations in density functional theory calculations: Energetics and structure of binary oxides

Hinuma, Yoyo; Hayashi, Hiroyuki; Kumagai, Yu; Tanaka, Isao; Oba, Fumiyasu

doi:10.1103/physrevb.96.094102

Cited by 116 publications

(94 citation statements)

References 160 publications

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“…for BeO the energy is calculated to be 0.11 eV/atom for all three functionals, which agrees exactly with the value reported in Ref. [42] obtained from more expensive phonon calculations. In the rest of the article, the sum of the zero-point and thermal contributions is denoted as the vibrational contribution.…”

Section: Methodssupporting

confidence: 89%

Coordination corrected ab initio formation enthalpies

et al. 2019

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The correct calculation of formation enthalpy is one of the enablers of ab-initio computational materials design. For several classes of systems (e.g. oxides) standard density functional theory produces incorrect values. Here we propose the "Coordination Corrected Enthalpies" method (CCE), based on the number of nearest neighbor cation-anion bonds, and also capable of correcting relative stability of polymorphs. CCE uses calculations employing the Perdew, Burke and Ernzerhof (PBE), Local Density Approximation (LDA) and Strongly Constrained and Appropriately Normed (SCAN) exchange correlation functionals, in conjunction with a quasiharmonic Debye model to treat zero-point vibrational and thermal effects. The benchmark, performed on binary and ternary oxides (halides), shows very accurate room temperature results for all functionals, with the smallest mean absolute error of 27 (24) meV/atom obtained with SCAN. The zero-point vibrational and thermal contributions to the formation enthalpies are small and with different signs -largely cancelling each other.

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Section: Methodssupporting

confidence: 89%

Coordination corrected ab initio formation enthalpies

et al. 2019

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“…The discrepancy in the magnetic ground-state configuration predicted by SCAN+U may be attributed to the specific AFM ordering used in our calculations, which was originally proposed by Regulski et al 77 Note that the ground-state AFM ordering of -Mn2O3 is still debated. 76,77 Also, the small difference in energy between the FM and AFM -Mn2O3 configurations (25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38)(39)(40) (Figure 5b and d). Experimentally, -Mn2O3 exhibits a band gap of 1.…”

Section: Lattice Parameters and Band Gapsmentioning

confidence: 99%

Evaluating transition metal oxides within DFT-SCAN and SCAN+U frameworks for solar thermochemical applications

Gautam

Carter

2018

Phys. Rev. Materials

129

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Using the strongly constrained and appropriately normed (SCAN) and SCAN+U approximations for describing electron exchange-correlation (XC) within density functional theory, we investigate the oxidation energetics, lattice constants, and electronic structure of binary Ce-, Mn-, and Fe-oxides, which are crucial ingredients for generating renewable fuels using two-step, oxide-based, solar thermochemical reactors. Unlike other common XC functionals, we find that SCAN does not over-bind the O2 molecule, based on direct calculations of its bond energy and robust agreement between calculated formation enthalpies of main group oxides versus experiments. However, in the case of transition-metal oxides (TMOs), SCAN systematically overestimates (i.e., yields too negative) oxidation enthalpies due to remaining self-interaction errors in the description of their ground-state electronic structure. Adding a Hubbard U term to the transition-metal centers, where the magnitude of U is determined from experimental oxidation enthalpies, significantly improves the qualitative agreement and marginally improves the quantitative agreement of SCAN+U-calculated electronic structure and lattice parameters, respectively, with experiments. Importantly, SCAN predicts the wrong ground-state structure for a few oxides, namely, Ce2O3, Mn2O3, and Fe3O4, while SCAN+U predicts the right polymorph for all systems considered in this work. Hence, the SCAN+U framework, with an appropriately determined U, will be required to accurately describe ground-state properties and yield qualitatively consistent electronic properties for most transitionmetal and rare earth oxides.

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“…This definition of the total energy [Eq. (13)] can be used to evaluate derivatives with respect to n I . Based on these definitions, the first and second derivatives give:…”

Section: Hubbard U From Linear-response Constrained Dftmentioning

confidence: 99%

Hubbard parameters from density-functional perturbation theory

2018

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We present a transparent and computationally efficient approach for the first-principles calculation of Hubbard parameters from linear-response theory. This approach is based on density-functional perturbation theory and the use of monochromatic perturbations. In addition to delivering much improved efficiency, the present approach makes it straightforward to calculate automatically these Hubbard parameters for any given system, with tight numerical control on convergence and precision. The effectiveness of the method is showcased in three case studies -Cu2O, NiO, and LiCoO2 -and by the direct comparison with finite differences in supercell calculations. I. INTRODUCTIONThe development of density-functional theory (DFT) [1,2] has allowed modeling of a broad spectrum of properties for a large variety of systems. In practical applications DFT relies on approximations to the exchange-correlation (xc) electronic interactions, among which the local-density approximation (LDA) and the generalized-gradient approximation (GGA) are the most popular ones. Both approximations suffer from self-interaction errors (SIE), which limit the accuracy only to systems with weak and moderate electronic correlations. In systems with strongly localized electrons of d and f types, SIE in LDA and GGA are much larger, which leads to overdelocalization of these electrons and quantitative and sometimes even qualitative failures in the description of complex materials (e.g. metallic instead of insulating ground states).Various corrective methods have been devised to deal with SIE. In particular, in DFT with hybrid functionals -such as e.g. B3LYP [3][4][5][6][7] or HSE06 [8,9] -a fraction of the non-local Fock exchange is used for all (strongly localized and non-strongly localized) electrons with a fraction of (semi-)local exchange and a fully (semi-)local correlation. This approach is computationally more expensive than DFT with (semi-)local functionals, because the Fock exchange is a non-local integral operator which acts on Kohn-Sham (KS) wave functions. However, there has been recent progress in the development of very efficient techniques, such as the adaptively compressed exchange [10], to speed up such calculations. Another recent suggestion is the meta-GGA functional SCAN (strongly constrained and appropriately normed semilocal density functional) [11], which has shown promising results for many systems [12,13]. Having a marginal increase in the computational cost, DFT with the SCAN functional uses a xc potential which depends on KS wave functions via a kinetic energy density. However, SCAN still contains significant SIE [12]. arXiv:1805.01805v2 [cond-mat.str-el]

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Comparison of approximations in density functional theory calculations: Energetics and structure of binary oxides

Cited by 116 publications

References 160 publications

Coordination corrected ab initio formation enthalpies

Coordination corrected ab initio formation enthalpies

Evaluating transition metal oxides within DFT-SCAN and SCAN+U frameworks for solar thermochemical applications

Hubbard parameters from density-functional perturbation theory

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