Tkatchenko-Scheffler van der Waals correction method with and without self-consistent screening applied to solids

• Published in: Physical review. B, Condensed matter and materials physics Vol. 87; no. 6
• Main Authors: Bučko, Tomáš, Lebègue, S., Hafner, Jürgen, Ángyán, J. G.
• Format: Journal Article
• Language: English
• Published: American Physical Society 01-02-2013
• Subjects: Binding energy; Chemical Sciences; Condensed matter; Cristallography; Crystal structure; Density; Graphite; Mathematical analysis; Molybdenum disulfide; Zinc
• ISSN: 1098-0121; 1550-235X
• DOI: 10.1103/PhysRevB.87.064110

The method proposed by Tkatchenko and Scheffler [Phys. Rev. Lett. 102, 073005 (2009) (http://dx.doi.org/10.1103/PhysRevLett. 102.073005)] to correct density functional calculations for the missing van der Waals interactions is implemented in the Vienna ab initio simulation package (VASP) code and tested on a wide range of solids, including noble-gas crystals, molecular crystals ( alpha -N sub(2), sulfur dioxide, benzene, naphthalene, cytosine), layered solids (graphite, hexagonal boron nitride, vanadium pentoxide, MoS sub(2), NbSe sub(2)), chain-like structures (selenium, tellurium, cellulose I), ionic crystals (NaCl, KI), and metals (nickel, zinc, cadmium). In addition to the original formulation expressing the van der Waals (vdW) corrections as pairwise potentials whose strength is derived from the rescaled polarizabilities of the neutral free atoms, the self-consistently screened ( TS + SCS ) [Phys. Rev. Lett. 108. 236402 (2012) (http://dx.doi.org/10.1103/PhysRevLett. 108.236402)] variant of the method involving electrodynamic response effects has been examined. Analytical expressions for the forces acting on the atoms and for the components of the stress tensor needed for the relaxation of the volume and shape of the unit cell using the TS + SCS method are derived. While the calculated structures are reasonably close to experiment, the van der Waals corrections to the binding energies are often found to be overestimated in comparison with experimental data. The TS + SCS approach leads to significantly better results in some problematic cases, such as the binding energy of graphite. However, there is room for further improvements, in particular for strongly ionic systems.