On the Importance of Gradient-Corrected Correlation for van der Waals Density Functionals
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The van der Waals density functional (vdW-DF) family of exchange–correlation functionals is a promising step towards accounting for van der Waals interactions in density functional theory. This approach consists of a nonlocal correlation term in addition to semilocal generalized gradient approximation exchange and local density approximation correlation. It has proven useful for describing vdW bonded complexes but unfortunately deteriorates the prediction of solid-state properties such as bulk lattice parameters and cohesive energies, as compared to the underlying GGA functional. By considering a broad range of different condensed matter systems including weakly interacting complexes as well as strongly bonded molecules and bulk solids, we show that inclusion of gradient-corrected correlations in vdW-DF-type calculations may not only improve the accuracy for vdW bonded systems, but also amend vdW-DF deficiencies in predicting structural properties of solids. Based on this insight we construct a prototype vdW-DF which demonstrates high accuracy in describing the dispersive interactions responsible for benzene adsorption on the noble Au(111) surface.
KeywordsDensity functional theory van der Waals vdW-DF RPBE + nl RPBEc2/3 + nl Au(111) Benzene
The Center for Atomic-scale Materials Design is funded by the Lundbeck Foundation. We acknowledge support from the Danish Center for Scientific Computing. Support from the U.S. Department of Energy, Office of Basic Energy Sciences is gratefully acknowledged.
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