On the accuracy of DFT exchange-correlation functionals for H bonds in small water clusters II: The water hexamer and van der Waals interactions

TL;DR

This study evaluates the accuracy of various DFT exchange-correlation functionals in predicting the energies and orderings of water hexamer isomers, highlighting the importance of van der Waals interactions and improvements via empirical corrections.

Contribution

The paper provides a detailed assessment of DFT functionals against high-level reference methods for water hexamers, emphasizing the role of dispersion forces and proposing empirical corrections.

Findings

DFT functionals fail to predict correct isomer energy ordering.

Van der Waals interactions are poorly described by standard DFT functionals.

Adding empirical C6/R6 corrections improves energetic predictions.

Abstract

Second order Moeller-Plesset perturbation theory (MP2) at the complete basis set (CBS) limit and diffusion quantum Monte Carlo (DMC) are used to examine several low energy isomers of the water hexamer. Both approaches predict the so-called "prism" to be the lowest energy isomer, followed by "cage", "book", and "cyclic" isomers. The energies of the four isomers are very similar, all being within 10-15 meV/H2O. This reference data is then used to evaluate the performance of several density-functional theory (DFT) exchange-correlation (xc) functionals. A subset of the xc functionals tested for smaller water clusters [I: Santra et al., J. Chem. Phys. 127, 184104 (2007)] has been considered. Whilst certain functionals do a reasonable job at predicting the absolute dissociation energies of the various isomers (coming within 10-20 meV/H2O), none predict the correct energetic ordering of the four isomers, nor does any predict the correct low total energy isomer. All xc functionals tested either predict the book or cyclic isomers to have the largest dissociation energies. A many-body decomposition of the total interaction energies within the hexamers leads to the conclusion that the failure lies in the poor description of van der Waals (dispersion) forces in the xc functionals considered. It is shown that the addition of an empirical pairwise (attractive) C6/R6 correction to certain functionals allows for an improved energetic ordering of the hexamers. The relevance of these results to density-functional simulations of liquid water is also briefly discussed.