English

van der Waals density functional with corrected $C_6$ coefficients

Materials Science 2019-05-21 v1 Atomic and Molecular Clusters Chemical Physics

Abstract

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 C6C_6 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 C6C_6 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 C6C_6 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\omega_{\mathbf{q}}, 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 C6C_6 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 C6C_6 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.

Keywords

Cite

@article{arxiv.1905.07757,
  title  = {van der Waals density functional with corrected $C_6$ coefficients},
  author = {K. Berland and D. Chakraborty and T. Thonhauser},
  journal= {arXiv preprint arXiv:1905.07757},
  year   = {2019}
}
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