The random phase approximation applied to ice
arXiv:1405.3977 · doi:10.1063/1.4865748
Abstract
Standard density functionals without van der Waals interactions yield an unsatisfactory description of ice phases, specifically, high density phases occurring under pressure are too unstable compared to the common low density phase I observed at ambient conditions. Although the description is improved by using functionals that include van der Waals interactions, the errors in relative volumes remain sizable. Here we assess the random phase approximation (RPA) for the correlation energy and compare our results to experimental data as well as diffusion Monte Carlo data for ice. The RPA yields a very balanced description for all considered phases, approaching the accuracy of diffusion Monte Carlo in relative energies and volumes. This opens a route towards a concise description of molecular water phases on surfaces and in cavities.
References in corpus (8)
- Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
- A molecular perspective of water at metal interfaces
- Nuclear quantum effects in water
- The role of van der Waals forces in water adsorption on metals
- On the accuracy of DFT exchange-correlation functionals for H bonds in small water clusters II: The water hexamer and van der Waals interactions
- On how good DFT exchange-correlation functionals are for H bonds in small water clusters: Benchmarks approaching the complete basis set limit
- To wet or not to wet? Dispersion forces tip the balance for water-ice on metals
- Coupled cluster benchmarks of water monomers and dimers extracted from DFT liquid water: the importance of monomer deformations