DFT modeling intermolecular interactions

Question

Density Functional Theory based codes evaluate quite successfully intramolecular forces responsible of the atomic bonding. Within this technique one is able to obtain molecular relaxed structures that match almost perfectly the experimentally measured geometry. This is particularly true for very diluted single molecule structures in which the intermolecular interactions are almost negligible.

My question arises regarding the non-covalent intermolecular interactions appearing in molecular solids (Hydrogen bonding, ion-dipole forces, dipolar (and quadrupolar) interaction, van der Waals interaction, London forces, among others).

What is the correct formulation of DFT to include such forces in the calculation thus producing an adequate result in structural modeling of new molecular materials?

Answer 1

They are included in long range type functionals. Here are some references:

• S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, J. Comput. Chem. 27 (2006) 1787.
• M. Dion, H. Rydberg, E. Schroder, D. Langreth, B. Lundqvist, Van der Waals density functional for general geometries, Phys. Rev. Lett. 92 (2004) 246401.
• G. Roman-Perez, J.M. Soler, Efficient implementation of a van der Waals density functional: application to double-wall carbon nanotubes, Phys. Rev. Lett. 103 (2009) 096102.
• J. Klimes, D.R. Bowler, A. Michaelides, Chemical accuracy for the van der Waals density functional, J. Phys. Condens. Matter 22 (2010) 022201.
• K. Lee, Eamonn D. Murray, L. Kong, B.I. Lundqvist, D.C. Langreth, Higher-accuracy van der Waals density functional, Phys. Rev. B 82 (2010) 081101.
• J.F. Dobson, T. Gould, Calculation of dispersion energies, J. Phys. Condens. Matter 24 (2012) 073201.
• D.-L. Chen, W.A. Al-Saidi, J.K. Johnson, The role of van der Waals interactions in the adsorption of noble gases on metal surfaces, J. Phys. Condens. Matter 24 (2012) 424211.