Nonempirical range-separated hybrid functionals for solids and molecules

Skone, Jonathan H.; Govoni, Marco; Galli, Giulia

doi:10.1103/physrevb.93.235106

Cited by 146 publications

(204 citation statements)

References 103 publications

(85 reference statements)

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“…Although computationally expensive, the use of the hybrid PBE0 functional avoids the parameterization necessary for the quantitatively reliable implementation of the PBE+U method for this type of system. The use of PBE0 is further motivated by recent calculations suggesting that the mixing fraction of exact exchange in global hybrid functionals should be chosen to be the inverse of the dielectric constant (32)(33)(34). The highfrequency dielectric constant was computed to be ∼3.5 for bulk Ni(OH) 2 (35), suggesting a fraction of exact exchange of 0.29, comparable to the fraction of 0.25 for PBE0.…”

Section: Resultsmentioning

confidence: 99%

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

Goldsmith

Harshan

Gerken

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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183

161

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NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni 2+ to Ni 3+ , followed by oxidation to a mixed Ni 3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe 4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.NiFe oxyhydroxide | oxygen evolution reaction | electrocatalysis | spectroelectrochemistry | density functional theory T he photoelectrochemical conversion of water into O 2 and H 2 is a major focus of energy storage and conversion efforts (1-4), with significant attention directed toward development of efficient catalysts for water oxidation and reduction. Such catalysts should operate at low overpotential, exhibit high selectivity, and be composed of earth-abundant materials. Commercial electrolyzers typically use transition-metal-oxide electrocatalysts for the oxygen evolution reaction (OER) (5, 6), and nickel, nickel-iron, and other mixed-metal oxides are especially effective under alkaline conditions (7,8). Despite the importance and potential future impact of these materials, many features of their catalytic mechanism are poorly understood.Nickel oxyhydroxide has long been associated with OER electrocatalysis (9, 10); however, much of the activity in this material has been shown to arise from the presence of Fe impurities (7, 11). This conclusion complements extensive independent studies demonstrating the effectiveness of NiFebased oxide and oxyhydroxide materials as OER electrocatalysts (12-14), including a survey of nearly 3,500 mixed-metal-oxide compositions, which drew attentio...

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Section: Resultsmentioning

confidence: 99%

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

Goldsmith

Harshan

Gerken

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

183

161

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“…The range-separation parameter μ can be obtained through standard least-squares fitting to the dielectric function ε −1 G,G (q → 0, ω = 0) in the long-wavelength limit, as done in Ref. [56]. The inverse macroscopic dielectric constant ε −1 ∞ corresponds to the G = 0 component of the dielectric function.…”

Section: A Generalized Range-separated Hybrid Functional With Dielecmentioning

confidence: 99%

“…The scheme was later adapted to extended systems [54,55]. In the more recent range-separated DDH (RS-DDH) of Skone et al [56], the screening length of Fock exchange is determined through the dielectric function calculated from first principles. Yet, the fraction of Fock exchange in RS-DDH is pinned at 25% in the short range on an empirical basis.…”

Section: Introductionmentioning

confidence: 99%

Nonempirical dielectric-dependent hybrid functional with range separation for semiconductors and insulators

Chen

Miceli

Rignanese

et al. 2018

Phys. Rev. Materials

142

148

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We present a general scheme of range-separated hybrid functionals in which the mixing parameters of Fock exchange are fully nonempirical and determined solely from the dielectric function.We showthat the full dielectric dependence leads to an unscreened Fock exchange in the short range, while in the long range the Fock exchange is correctly screened by the macroscopic dielectric constant. The range separation is obtained by fitting to the calculated static dielectric function in the long-wavelength limit. The resulting hybrid functional accurately accounts for electronic and structural properties of various semiconductors and insulators spanning a wide range of band gaps. We present a general scheme of range-separated hybrid functionals in which the mixing parameters of Fock exchange are fully nonempirical and determined solely from the dielectric function. We show that the full dielectric dependence leads to an unscreened Fock exchange in the short range, while in the long range the Fock exchange is correctly screened by the macroscopic dielectric constant. The range separation is obtained by fitting to the calculated static dielectric function in the long-wavelength limit. The resulting hybrid functional accurately accounts for electronic and structural properties of various semiconductors and insulators spanning a wide range of band gaps.

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“…254 Galli and coworkers have developed a dielectric-dependent range-separated hybrid that shows good accuracy for energy gaps of inorganic and organic solids. 255 In order to reap the benefits of both LC and SX functionals, it has been suggested to use three-ranges, with X increasing from short range to middle range and then decreasing from middle range to long range. 256 Another way to use range separation has nothing to do with Hartree-Fock exchange.…”

Section: Exchange-correlation Functionals Classified By Their Ingrmentioning

confidence: 99%

The behavior of active diffusiophoretic suspensions: An accelerated Laplacian dynamics study

Yan

Brady

2016

The Journal of Chemical Physics

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This article presents a perspective on Kohn-Sham density functional theory (KS-DFT) for electronic structure calculations in chemical physics. This theory is in widespread use for applications to both molecules and solids. We pay special attention to several aspects where there are both concerns and progress toward solutions. These include: 1. The treatment of open-shell and inherently multiconfigurational systems (the latter are often called multireference systems and are variously classified as having strong correlation, near-degeneracy correlation, or high static correlation; KS-DFT must treat these systems with broken-symmetry determinants). 2. The treatment of noncovalent interactions. 3. The choice between developing new functionals by parametrization, by theoretical constraints, or by a combination. 4. The ingredients of the exchange-correlation functionals used by KS-DFT, including spin densities, the magnitudes of their gradients, spin-specific kinetic energy densities, nonlocal exchange (Hartree-Fock exchange), nonlocal correlation, and subshell-dependent corrections (DFT+U). 5. The quest for a universal functional, where we summarize some of the success of the latest Minnesota functionals, namely MN15-L and MN15, which were obtained by optimization against diverse databases. 6. Time-dependent density functional theory, which is an extension of DFT to treat time-dependent problems and excited states. The review is a snapshot of a rapidly moving field, and-like Marcel Duchamp-we hope to convey progress in a stimulating way. Published by AIP Publishing. [http://dx

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Nonempirical range-separated hybrid functionals for solids and molecules

Cited by 146 publications

References 103 publications

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

Nonempirical dielectric-dependent hybrid functional with range separation for semiconductors and insulators

The behavior of active diffusiophoretic suspensions: An accelerated Laplacian dynamics study

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