We applied our new self-consistent polarization density functional theory (SCP-DFT) to liquid water. SCP-DFT requires only minimal parametrization, self-consistently includes the dispersion interaction neglected by standard DFT functionals, and has a cost similar to standard DFT despite its improved performance. Compared to the DFT functionals BLYP and BLYP-D (where the latter contains a simple dispersion correction), SCP-DFT yields cohesion energies and harmonic frequencies of clusters in better agreement with experiment, with errors in cohesion energies of only a few tenths of a kcal/mol. BLYP and BLYP-D underbind and overbind the clusters, respectively, by up to about 1 kcal/mol. For liquid water, SCP-DFT predicts radial distribution functions and enthalpy in better agreement with experiment than does BLYP. A decomposition of the dimer interaction energy rationalizes the good performance of SCP-DFT. The SCP-DFT approach holds promise as a fast, efficient, and accurate method for describing large hydrogen-bonded systems, and has the potential to model reactive processes.

Improving the DFT description of liquid water by the SCP-DFT method

239th National Meeting (2010)

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