Van der Waals density functional theory with applications

Langreth, David C.; Dion, Maxime; Rydberg, Henrik; Schröder, Elsebeth; Hyldgaard, Per; Lundqvist, Bengt I.

doi:10.1002/qua.20315

Cited by 328 publications

(379 citation statements)

References 42 publications

Supporting

Mentioning

365

Contrasting

Order By: Relevance

“…For the more compact C2 phase, our vdW-DF calculations of the direct vdW binding indicate a preference for a lattice constant of 6.9 Å. Given the tendency of the vdW-DF method to slightly overestimate binding separations, 21,28 this result suggests that the C2 phase can be interpreted as a direct, vdW-bound molecular-lattice structure. Explicit vdW-DF predictions of the preferred Bz orientations and of rotational barriers may offer experimental tests of this interpretation.…”

Section: Introductionmentioning

confidence: 74%

Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111)

2009

Self Cite

View full text Add to dashboard Cite

Using a van der Waals density functional ͑vdW-DF͒ ͓Phys. Rev. Lett. 92, 246401 ͑2004͔͒, we perform ab initio calculations for the adsorption energy of benzene ͑Bz͒ on Cu͑111͒ as a function of lateral position and height. We find that the vdW-DF inclusion of nonlocal correlations ͑responsible for dispersive interactions͒ changes the relative stability of eight binding-position options and increases the binding energy by over an order of magnitude, achieving good agreement with experiment. The admolecules can move almost freely along a honeycomb web of "corridors" passing between fcc and hcp hollow sites via bridge sites. Our diffusion barriers ͑for dilute and two condensed adsorbate phases͒ are consistent with experimental observations. Further vdW-DF calculations suggest that the more compact ͑hexagonal͒ Bz-overlayer phase, with lattice constant a = 6.74 Å, is due to direct Bz-Bz vdW attraction, which extends to ϳ8 Å. We attribute the second, sparser hexagonal Bz phase, with a = 10.24 Å, to indirect electronic interactions mediated by the metallic surface state on Cu͑111͒. To support this claim, we use a formal Harris-functional approach to evaluate nonperturbationally the asymptotic form of this indirect interaction. Thus, we can account well for benzene self-organization on Cu͑111͒.

show abstract

Section: Introductionmentioning

confidence: 74%

Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111)

2009

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently a truly first-principles approach, which does not require any fitting parameters and still stays within the remit of DFT (the total energy of electrons is a unique functional of the electron density r(r)), was developed [50][51][52] and successfully applied to many systems. 48 In this method the energy functional has the form:…”

Section: Theoretical Background and Motivationmentioning

confidence: 99%

“…It is argued in ref. [50][51][52] that the revPBE density functional 53 is the best choice for the GGA flavor to be used in the vdW-DF since it predicts negligible or no binding in vdW complexes due to the exchange alone.…”

Section: Theoretical Background and Motivationmentioning

confidence: 99%

Role of van der Waals interaction in forming molecule-metal junctions: flat organic molecules on the Au(111) surface

Mura

Guļāns

Thonhauser

et al. 2010

Phys. Chem. Chem. Phys.

115

147

View full text Add to dashboard Cite

The self-assembly of flat organic molecules on metal surfaces is controlled, apart from the kinetic factors, by the interplay between the molecule-molecule and molecule-surface interactions. These are typically calculated using standard density functional theory within the generalized gradient approximation, which significantly underestimates nonlocal correlations, i.e. van der Waals (vdW) contributions, and thus affects interactions between molecules and the metal surface in the junction. In this paper we address this question systematically for the Au(111) surface and a number of popular flat organic molecules which form directional hydrogen bonds with each other. This is done using the recently developed first-principles vdW-DF method which takes into account the nonlocal nature of electron correlation [M. Dion et al., Phys. Rev. Lett. 2004, 92, 246401]. We report here a systematic study of such systems involving completely self-consistent vdW-DF calculations with full geometry relaxation. We find that the hydrogen bonding between the molecules is only insignificantly affected by the vdW contribution, both in the gas phase and on the gold surface. However, the adsorption energies of these molecules on the surface increase dramatically as compared with the ordinary density functional (within the generalized gradient approximation, GGA) calculations, in agreement with available experimental data and previous calculations performed within approximate or semiempirical models, and this is entirely due to the vdW contribution which provides the main binding mechanism. We also stress the importance of self-consistency in calculating the binding energy by the vdW-DF method since the results of non-self-consistent calculations in some cases may be off by up to 20%. Our calculations still support the usually made assumption of the molecule-surface interaction changing little laterally suggesting that single molecules and their small clusters should be quite mobile at room temperature on the surface. These findings support a gas-phase modeling for some flat metal surfaces, such as Au(111), and flat molecules, at least as a first approximation.

show abstract

“…12 It is well known that GGA does not adequately describe vdW interactions, 33 thus if the layers of V 2 O 5 are mostly bound to each other by vdW forces it is not surprising that GGA calculations do not give physically reasonable results. In the following we report our results from GGA calculations, from vdW-DF calculations, and discuss the effect of exchange and the binding character of V 2 O 5 .…”

Section: Resultsmentioning

confidence: 99%

“…The correlation energy E c is split 33 into a nearly local part E c 0 and a part that includes the most nonlocal interactions E c nl ,…”

Section: B Vdw Density Functionalmentioning

confidence: 99%

Role of van der Waals bonding in the layered oxideV2O5: First-principles density-functional calculations

Londero

Schröder

2010

Phys. Rev. B

View full text Add to dashboard Cite

Sparse matter is characterized by regions with low electron density and its understanding calls for methods to accurately calculate both the van der Waals ͑vdW͒ interactions and other bonding. Here we present a first-principles density-functional theory ͑DFT͒ study of a layered oxide ͑V 2 O 5 ͒ bulk structure which shows charge voids in between the layers and we highlight the role of the vdW forces in building up material cohesion. The result of previous first-principles studies involving semilocal approximations to the exchangecorrelation functional in DFT gave results in good agreement with experiments for the two in-plane lattice parameters of the unit cell but overestimated the parameter for the stacking direction. To recover the third parameter we include the nonlocal ͑dispersive͒ vdW interactions through the vdW-DF method ͓M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 ͑2004͔͒ testing also various choices of exchange forms. We find that the transferable first-principles vdW-DF calculations stabilizes the bulk structure. The vdW-DF method gives results in fairly good agreement with experiments for all three lattice parameters.

show abstract

Van der Waals density functional theory with applications

Cited by 328 publications

References 42 publications

Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111)

Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111)

Role of van der Waals interaction in forming molecule-metal junctions: flat organic molecules on the Au(111) surface

Role of van der Waals bonding in the layered oxideV2O5: First-principles density-functional calculations

Contact Info

Product

Resources

About