Van der Waals density functional: an appropriate exchange functional

By Valentino R. Cooper. 2009

392 citations recorded by the source corpus.

In this paper, an exchange functional which is compatible with the non-local Rutgers-Chalmers correlation functional (vdW-DF) is presented. This functional, when employed with vdW-DF, demonstrates remarkable improvements on intermolecular separation distances while further improving the accuracy of vdW-DF interaction energies. The key to the success of this three parameter functional is its reduction of short range exchange repulsion through matching to the gradient expansion approximation in the slowly varying/high density limit while recovering the large reduced gradient, s, limit set in the revised PBE exchange functional. This augmented exchange functional could be a solution to long-standing issues of vdW-DF lending to further applicability of density functional theory to the study of relatively large, dispersion bound (van der Waals) complexes. Van der Waals, or London dispersion, interactions have profound importance in bio-organic systems as well as many novel materials being investigated for energy applications. Despite the importance of these systems and applications, first principles simulations have been greatly lacking. The primary reason for this is the inability of traditional density functional theory exchangecorrelation functionals to account for long-ranged, van der Waals interactions. This has limited first-principles investigations to quantum chemical methods which, due to their computational expense, are only capable of modeling fragments of the true material; thus often overlooking some of the more salient features of these systems.

Subfields: Atomic and Molecular Physics, and Optics, Inorganic Chemistry

View Paper: https://www.semanticscholar.org/paper/298d009c5c40650f63caee0a726a7a6cce088c62

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In Atomic and Molecular Physics, and Optics

In Inorganic Chemistry

Citations in the corpus

van der Waals forces in density functional theory: a review of the vdW-DF method (2014, methodology): “vdW-DF calculations have been performed on all duplexes in the S22 data set and results are presented in [63, 80, 107, 108, 198, 199, 239].”
Materials perspective on Casimir and van der Waals interactions (2015, methodology): “The vdW-DF approach originated by Langreth, Lundqvist, and collaborators (Cooper et al., 2010; Dion et al., 2004; Lee et al., 2010) that has become widely used to correct semi-local DFAs can also be derived from Eq.”