Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional

Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo; Sun, Zhaoru; Ruzsinszky, Adrienn; Peng, Haowei; Yang, Zeng-hui; Paul, Arpita; Waghmare, Umesh V.; Wu, Xifan; Klein, Michael L.; Perdew, John P.

doi:10.1038/nchem.2535

Cited by 862 publications

(729 citation statements)

References 50 publications

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“…205 The value of the rangeseparation parameter is close to 1 when TS is coupled with the nonempirical PBE, PBE0, or HSE functional. Values slightly larger are obtained for meta-GGA functionals, 63,64,206 which confirms that these functionals can effectively describe electron correlation at intermediate interatomic distances.…”

Section: Chemical Reviewssupporting

confidence: 57%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation−dissipation (ACFD) theorem (namely the Rutgers−Chalmers vdW-DF, Vydrov−Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko−Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.

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Section: Chemical Reviewssupporting

confidence: 57%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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“…Asymptotes in the probability of recovery are due to unique structural prototypes in the validation data set that are not in the training data set. electronic structures, 58 and exhibits more accurate polymorph energy rankings for some transition metal oxides. 59 Figure 5 shows SCAN nitride formation energies benchmarked against known experimental formation energies of binary nitrides, yielding an RMSE = 0.099 eV/ atom.…”

Section: ■ Methodsmentioning

confidence: 99%

Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides

et al. 2017

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Compared to oxides, the nitrides are relatively unexplored, making them a promising chemical space for novel materials discovery. Of particular interest are nitrogen-rich nitrides, which often possess useful semiconducting properties for electronic and optoelectronic applications. However, such nitrogen-rich compounds are generally metastable, and the lack of a guiding theory for their synthesis has limited their exploration. Here, we review the remarkable metastability of observed nitrides, and examine the thermodynamics of how reactive nitrogen precursors can stabilize metastable nitrogen-rich compositions during materials synthesis. We map these thermodynamic strategies onto a predictive computational search, training a data-mined ionic substitution algorithm specifically for nitride discovery, which we combine with grand-canonical DFT-SCAN phase stability calculations to compute stabilizing nitrogen chemical potentials. We identify several new nitrogen-rich binary nitrides for experimental investigation, notably the transition metal nitrides Mn 3 N 4 , Cr 3 N 4 , V 3 N 4 , and Nb 3 N 5 , the main group nitride SbN, and the pernitrides FeN 2 , CrN 2 , and Cu 2 N 2 . By formulating rational thermodynamic routes to metastable compounds, we expand the search space for functional technological materials beyond equilibrium phases and compositions.

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“…The recently-developed nonempirical strongly constrained and appropriately normed semilocal density functional (SCAN) has been shown to estimate accurate structures and energetics of diversely bonded molecules and materials (for slowly as well as rapidly varying electron densities) and to improve the band gap, which was underestimated by LDA and GGA [18][19][20][21] . The SCAN meta-GGA satisfies all the 17 known exact constraints (about 6 for exchange, 6 for correlation and 5 for the sum of two) appropriate to semilocal functionals by including the orbital kinetic energy densities 18 .…”

Section: Introductionmentioning

confidence: 99%

Accuracy of first-principles interatomic interactions and predictions of ferroelectric phase transitions in perovskite oxides: Energy functional and effective Hamiltonian

et al. 2017

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While first-principles density functional theory (DFT) based models have been effective in capturing the physics of ferroelectric phase transitions in BaTiO 3 , PbTiO 3 and KNbO 3 , quantitative estimates of the transition temperatures (T C 's) suffer from errors that are believed to originate from the errors in estimating lattice constants obtained within local density (LDA) and gradient density (GGA) approximations of DFT. The recently-developed strongly constrained and appropriately normed (SCAN) meta-GGA functional has been shown to be quite accurate in estimation of lattice constants. Here, we present a quantitative analysis of the estimates of ferroelectric ground state properties of eight perovskite oxides and transition temperatures of BaTiO 3 , PbTiO 3 and KNbO 3 obtained with molecular dynamics (MD) simulations using an effective Hamiltonian derived from the SCAN meta-GGA based DFT. Relative to LDA, we find an improvement in estimates of T C 's, which arises from the changes in calculated strain-phonon, anharmonic coupling constants and strength of ferroelectric instabilities, i.e., frequencies of the soft modes. We also assess the errors in T C originating from approximately integrating out the high-energy phonons during construction of the model Hamiltonian through estimates of the effects of fourth-order couplings between soft mode and higher energy modes of BaTiO 3 , PbTiO 3 and KNbO 3 . We find that inclusion of these anharmonic couplings results in deeper double-well energy functions of ferroelectric distortions and further improvement in the estimates of transition temperatures. Consistently improved estimates of lattice constants and transition temperatures with the SCAN meta-GGA calculations augur well for their use in simulations of superlattices or hetero-structures of perovskite oxides, in which the effects of lattice matching are critical.

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Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional

Cited by 862 publications

References 50 publications

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides

Accuracy of first-principles interatomic interactions and predictions of ferroelectric phase transitions in perovskite oxides: Energy functional and effective Hamiltonian

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