Signatures of van der Waals binding: A coupling-constant scaling analysis

Jiao, Yang; Schröder, Elsebeth; Hyldgaard, Per

doi:10.1103/physrevb.97.085115

Cited by 25 publications

(86 citation statements)

References 140 publications

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“…However, at binding separations such higher-order terms are generally less crucial, at least within vdW-DF, 30,57 as multipole effects are described to second order in S. Moreover, vdW-DF includes non-additive effects originating from changes in the electronic density. 58 Drawing attention to the possibility of adjusting h(y) within vdW-DF introduces a measure of flexibility that so far has been missing in standard vdW-DF. In fact, since the release of vdW-DF1 in 2004, 14 a number of exchange functionals have been proposed that aim both to improve binding energies and remedy the notorious overestimation of binding separations present in vdW-DF1 and to some extent in vdW-DF2.…”

Section: Discussionmentioning

confidence: 99%

van der Waals density functional with corrected C6 coefficients

2019

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The non-local van der Waals density functional (vdW-DF) has had tremendous success since its inception in 2004 due to its constraint-based formalism that is rigorously derived from a many-body starting point. However, while vdW-DF can describe binding energies and structures for van der Waals complexes and mixed systems with good accuracy, one long-standing criticism-also since its inception-has been that the C6 coefficients that derive from the vdW-DF framework are largely inaccurate and can be wrong by more than a factor of two. It has long been thought that this failure to describe the C6 coefficients is a conceptual flaw of the underlying plasmon framework used to derive vdW-DF. We prove here that this is not the case and that accurate C6 coefficient can be obtained without sacrificing the accuracy at binding separations from a modified framework that is fully consistent with the constraints and design philosophy of the original vdW-DF formulation. Our design exploits a degree of freedom in the plasmon-dispersion model ωq, modifying the strength of the long-range van der Waals interaction and the cross-over from long to short separations, with additional parameters tuned to reference systems. Testing the new formulation for a range of different systems, we not only confirm the greatly improved description of C6 coefficients, but we also find excellent performance for molecular dimers and other systems. The importance of this development is not necessarily that particular aspects such as C6 coefficients or binding energies are improved, but rather that our finding opens the door for further conceptual developments of an entirely unexplored direction within the exact same constrained-based non-local framework that made vdW-DF so successful in the first place.

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Section: Discussionmentioning

confidence: 99%

van der Waals density functional with corrected C6 coefficients

2019

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“…The vdW-DF-cx description of the fullerene crystals gives an example: Appendix A shows that vdW-DF-cx does give an accurate description of structural motifs in fullerene crystals at binding separation even if vdW-DF-cx is not accurate for (and does not give nonadditive) C 6 coefficients, Table VII. We also note that the vdW-DFcx is nonadditive in a different sense, namely in its description of the nonlocal correlation interaction at binding separations [69].…”

Section: Appendix B: Asymptotic Binding In Vdw-df-cxmentioning

confidence: 97%

First-principles study of the binding energy between nanostructures and its scaling with system size

Tao

Jiao

et al. 2018

Phys. Rev. B

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The equilibrium van der Waals binding energy is an important factor in the design of materials and devices. However, it presents great computational challenges for materials built up from nanostructures. Here we investigate the binding-energy scaling behavior from first-principles calculations. We show that the equilibrium binding energy per atom between identical nanostructures can scale up or down with nanostructure size, but can be parametrized for large N with an analytical formula (in meV/atom), E b /N = a + b/N + c/N 2 + d/N 3 , where N is the number of atoms in a nanostructure and a, b, c, and d are fitting parameters, depending on the properties of a nanostructure. The formula is consistent with a finite large-size limit of binding energy per atom. We find that there are two competing factors in the determination of the binding energy: Nonadditivities of van der Waals coefficients and center-to-center distance between nanostructures. To decode the detail, the nonadditivity of the static multipole polarizability is investigated from an accurate spherical-shell model. We find that the higher-order multipole polarizability displays ultrastrong intrinsic nonadditivity, no matter if the dipole polarizability is additive or not.

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“…Both VV10 and rVV10 have two adjustable parameters b and c assuring the compatibility between the semilocal XC functional and E nl c [n]. Recently, several variations of these vdW functionals have been proposed: AM05-VV10sol [40], SCAN+rVV10 [41], PBE+rVV10L [42], SG4+rVV10m [43], C09-vdW-DF [44], vdW-DF-cx [45][46][47][48], PBEsol+rVV10s [49], and rev-vdW-DF2 [50,51]. All these variations have been tested for many vdW systems, such as layered materials [33,[39][40][41][42]45,49,[51][52][53][54][55][56][57][58][59][60][61][62], rare-gas (RG) solids [43,49,62,63], and molecular solids [43,62].…”

Section: Introductionmentioning

confidence: 99%

“…In the case of SIESTA, we combine SG4 and PBEsol with VV10 (instead of rVV10), keeping the same dispersion parameters b and c. The SIESTA method, which uses localized numerical atomic orbitals (NAOs), has a number of advantages with respect to a plane-wave basis set: SIESTA is typically more efficient, as the number of required basis functions is usually smaller, and SIESTA's localized basis set gives a better description of systems where the orbitals are strictly localized in real space, as in the case of adsorption of atoms/molecules on surfaces and in the case of interfaces with different materials. Here we investigate, in the framework of the SIESTA method, new dispersion-corrected functionals that we call PBEsol+VV10s and SG4+VV10m, and we compare to the results one obtains with other functionals such as PBE+VV10L [42] and vdW-DF-cx [45][46][47][48].…”

Section: Introductionmentioning

confidence: 99%

Comparison of dispersion-corrected exchange-correlation functionals using atomic orbitals

et al. 2019

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for the adsorption of a noble-gas atom/monolayer as well as a graphene on the Cu(111), Pt(111), Pd(111), and Ag(111) close-packed surfaces. Most of these systems are characterized by weak interactions between the surface and the atom/monolayer, where the van der Waals interaction dominates. Here we investigate the above mentioned dispersion-corrected exchange-correlation functionals using atomic orbitals instead of plane waves applied in earlier works. We find that PBEsol+VV10s is an optimal functional for such hybrid interfaces, being accurate for both the equilibrium distance and the adsorption energy and providing realistic potential-energy curves. Moreover, we also show that PBEsol+VV10s and SG4+VV10m are both very accurate for the investigation of surface formation energies of all transition metals under consideration.

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Signatures of van der Waals binding: A coupling-constant scaling analysis

Cited by 25 publications

References 140 publications

van der Waals density functional with corrected C6 coefficients

van der Waals density functional with corrected C6 coefficients

First-principles study of the binding energy between nanostructures and its scaling with system size

Comparison of dispersion-corrected exchange-correlation functionals using atomic orbitals

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