mBEEF-vdW: Robust fitting of error estimation density functionals

Lundgaard, Keld T.; Wellendorff, Jess; Voss, Johannes; Jacobsen, Karsten Wedel; Bligaard, Thomas

doi:10.1103/physrevb.93.235162

Cited by 45 publications

(48 citation statements)

References 81 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…17,18 Functionals that incorporate nonlocal correlation in addition to semilocal correlation can describe long-range interactions. Examples of meta-GGAs in this category include mBEEF-vdW, 46 B97M-V, 22 and SCAN+rVV10. 47 The rVV10 correlation functional in particular was designed for efficient evaluation in extended solids.…”

Section: ■ Introductionmentioning

confidence: 99%

Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces

Garza

Bell

Head‐Gordon

2018

J. Chem. Theory Comput.

View full text Add to dashboard Cite

We assess the accuracy of popular nonempirical GGAs (PBE, PBEsol, RPBE) and meta-GGAs (TPSS, revTPSS, and SCAN) for describing chemisorption reactions at metal surfaces. Except for RPBE, all the functionals tend to overbind the adsorbate significantly. We then propose a nonempirical meta-GGA, denoted as RTPSS, that is based on RPBE in the same way that TPSS is based on PBE. The RTPSS functional remedies the overbinding problem and improves the description of chemisorption energies. As an example of an application of RTPSS, we study the adsorption of CO on Cu surfaces (a notably difficult problem for semilocal functionals) and find that RTPSS is the only tested functional that predicts accurate chemisorption energies and the preferred adsorption site of CO. Although RTPSS gives an accurate description of chemisorption, nonlocal correlation may be necessary to describe physisorption if long-range van der Waals interactions are involved (however, this is true for semilocal functionals in general). We suggest that RTPSS can be a useful meta-GGA for studying chemisorption processes and mechanisms of heterogeneous catalysis.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces

Garza

Bell

Head‐Gordon

2018

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…We cannot expect improvement of the Rutgers-Chalmers vdW-DF1 and vdW-DF2 methods by directly incorporating SCAN, either only in the exchange part or the whole semilocal exchange correlation energy. Other meta-GGAs [83,84] may provide better options for the semilocal part.…”

Section: B Vdw Corrections To Meta-ggamentioning

confidence: 99%

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

et al. 2016

View full text Add to dashboard Cite

A "best-of-both-worlds" van der Waals (vdW) density functional is constructed, seamlessly supplementing the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for short-and intermediate-range interactions with the long-range vdW interaction from rVV10, the revised Vydrov-van Voorhis nonlocal correlation functional. The resultant SCANþrVV10 is the only vdW density functional to date that yields excellent interlayer binding energies and spacings, as well as intralayer lattice constants in 28 layered materials. Its versatility for various kinds of bonding is further demonstrated by its good performance for 22 interactions between molecules; the cohesive energies and lattice constants of 50 solids; the adsorption energy and distance of a benzene molecule on coinage-metal surfaces; the binding energy curves for graphene on Cu(111), Ni(111), and Co (0001) surfaces; and the rare-gas solids. We argue that a good semilocal approximation should (as SCAN does) capture the intermediate-range vdW through its exchange term. We have found an effective range of the vdW interaction between 8 and 16 Å for systems considered here, suggesting that this interaction is negligibly small at the larger distances where it reaches its asymptotic power-law decay.

show abstract

“…Although special care has to be taken, [93][94][95] it can be coupled with dispersion-corrected functionals. 52,[96][97][98][99][100][101] Also, the same approach can be applied to correlation functionals, and we will also report results on this soon.…”

Section: Discussionmentioning

confidence: 99%

Exchange functionals based on finite uniform electron gases

Loos

2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

We show how one can construct a simple exchange functional by extending the wellknow local-density approximation (LDA) to finite uniform electron gases. This new generalized local-density approximation (GLDA) functional uses only two quantities: the electron density ρ and the curvature of the Fermi hole α. This alternative "rung 2" functional can be easily coupled with generalized-gradient approximation (GGA) functionals to form a new family of "rung 3" meta-GGA (MGGA) functionals that we INTRODUCTIONDue to its moderate computational cost and its reasonable accuracy, Kohn-Sham (KS) density-functional theory 1,2 (DFT) has become the workhorse of electronic structure calculations for atoms, molecules and solids. 3 To obtain accurate results within DFT, one only requires the exchange and correlation functionals, which can be classified in various families depending on their physical input quantities. 4,5 These various types of functionals are classified by the Jacob's ladder of DFT 6,7 (see Fig. 1). The local-density approximation (LDA) sits on the first rung of the Jacob's ladder and only uses as input the electron density ρ. The generalized-gradient approximation (GGA) corresponds to the second rung and adds the gradient of the electron density ∇ρ as an extra ingredient. The third rung is composed by the so-called meta-GGA (MGGA) functionals 8 which uses, in addition to ρ and ∇ρ, the kinetic energy density τ = occ i |∇ψ i | 2 (where ψ i is an occupied molecular orbital). The infinite uniform electron gas (IUEG) or jellium 9-13 is a much studied and wellunderstood model system, and hence a logical starting point for local exchange-correlation approximations. 14-22 Though analytical models are scarce, we have recently discovered an entire new family of analytical models that one can use to develop new exchange and correlation functionals within DFT. 23-29 Indeed, we have shown that, by constraining n electrons on a surface of a three-dimensional sphere (or 3-sphere), one can create finite uniform electron gases (FUEGs). 13,27,30 Here, we show how to use these FUEGs to create a new type of exchange functionals applicable to any type of systems. We have already successfully applied this strategy to one-dimensional systems, 28,31,32 for which we have created a correlation functional based on this idea. 25,26 Moreover, we show that these alternative second-rung functionals can be easily coupled to GGA functionals to form a new family of third-rung MGGA functionals. Unless otherwise stated, we use atomic units throughout. II. THEORYWithin DFT, one can write the total exchange energy as the sum of its spin-up (σ = ↑) and spin-down (σ = ↓) contributions:2 Hartree Rung 1:Rung 2:Rung 2 : whereand ρ σ is the electron density of the spin-σ electrons. Although, for sake of simplicity, we sometimes remove the subscript σ, we only use spin-polarized quantities from hereon.The first-rung LDA exchange functional (or D30 33 ) is based on the IUEG 13 and readswhere3 A GGA functional (second rung) is defined aswhere F GGA x is th...

show abstract

mBEEF-vdW: Robust fitting of error estimation density functionals

Cited by 45 publications

References 81 publications

Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces

Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

Exchange functionals based on finite uniform electron gases

Contact Info

Product

Resources

About