Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond

Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond

September 14, 2018 | T. Thonhauser, Valentino R. Cooper, Shen Li, Aaron Puzder, Per Hyldgaard, David C. Langreth
The paper derives the exchange-correlation potential corresponding to the nonlocal van der Waals (vdW) density functional, enabling self-consistent calculations of ground state properties for various systems. The authors apply this potential to van der Waals complexes and crystalline silicon, finding that the results are largely determined by semilocal exchange and correlation in the latter case, while the self-consistency effect is minimal in the former. The study validates previous calculations treating the fully nonlocal term as a post-GGA perturbation. The exchange-correlation potential also allows for the calculation of Hellmann-Feynman forces, facilitating efficient geometry relaxations and the use of standard techniques that depend on the self-consistent charge distribution. The nature of the van der Waals bond is discussed in terms of the self-consistent bonding charge, showing that the induced electron density changes significantly when the nonlocal contribution is included. The findings suggest that the vdW-DF theory is a general density functional, performing well for systems with substantial vdW forces but not affecting the results of ordinary LDA-GGA functionals when vdW forces are unimportant.The paper derives the exchange-correlation potential corresponding to the nonlocal van der Waals (vdW) density functional, enabling self-consistent calculations of ground state properties for various systems. The authors apply this potential to van der Waals complexes and crystalline silicon, finding that the results are largely determined by semilocal exchange and correlation in the latter case, while the self-consistency effect is minimal in the former. The study validates previous calculations treating the fully nonlocal term as a post-GGA perturbation. The exchange-correlation potential also allows for the calculation of Hellmann-Feynman forces, facilitating efficient geometry relaxations and the use of standard techniques that depend on the self-consistent charge distribution. The nature of the van der Waals bond is discussed in terms of the self-consistent bonding charge, showing that the induced electron density changes significantly when the nonlocal contribution is included. The findings suggest that the vdW-DF theory is a general density functional, performing well for systems with substantial vdW forces but not affecting the results of ordinary LDA-GGA functionals when vdW forces are unimportant.
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