A recent extensive study has investigated how various exchange-correlation (XC) functionals treat hydrogen bonds in water hexamers and has shown traditional generalized gradient approximation and hybrid functionals used in density-functional (DF) theory to give the wrong dissociation-energy trend of low-lying isomers and van der Waals (vdW) dispersion forces to give key contributions to the dissociation energy. The question raised whether functionals that incorporate vdW forces implicitly into the XC functional predict the correct lowest-energy structure for the water hexamer and yield accurate total dissociation energy is here answered affirmatively for the vdW-DF [M. Dion et al, Phys. Rev. Lett.92, 246401 (2004)].
Density functional for van der Waals forces accounts for hydrogen bond in benchmark set of water hexamers
André K. Kelkkanen, Bengt I. Lundqvist, Jens K. Nørskov; Density functional for van der Waals forces accounts for hydrogen bond in benchmark set of water hexamers. J. Chem. Phys. 28 July 2009; 131 (4): 046102. https://doi.org/10.1063/1.3193462
Download citation file: