Towards an assessment of the accuracy of density functional theory for first principles simulations of water

• Published in: The Journal of chemical physics 2004-01, Vol.120 (1), p.300-311
• Main Authors: Grossman, Jeffrey C, Schwegler, Eric, Draeger, Erik W, Gygi, François, Galli, Giulia
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1630560

A series of Car-Parrinello (CP) molecular dynamics simulations of water are presented, aimed at assessing the accuracy of density functional theory in describing the structural and dynamical properties of water at ambient conditions. We found negligible differences in structural properties obtained using the Perdew-Burke-Ernzerhof or the Becke-Lee-Yang-Parr exchange and correlation energy functionals; we also found that size effects, although not fully negligible when using 32 molecule cells, are rather small. In addition, we identified a wide range of values of the fictitious electronic mass (micro) entering the CP Lagrangian for which the electronic ground state is accurately described, yielding trajectories and average properties that are independent of the value chosen. However, care must be exercised not to carry out simulations outside this range, where structural properties may artificially depend on micro. In the case of an accurate description of the electronic ground state, and in the absence of proton quantum effects, we obtained an oxygen-oxygen correlation function that is overstructured compared to experiment, and a diffusion coefficient which is approximately ten times smaller.