We present herein a comprehensive density functional theory study toward assessing the accuracy of two popular gradient-corrected exchange correlation functionals on the structure and density of liquid water at near ambient conditions in the isobaric-isothermal ensemble. Our results indicate that both PBE and BLYP functionals under predict the density and over structure the liquid. Adding the dispersion correction due to Grimme (1, 2) improves the predicted densities for both BLYP and PBE in a significant manner. Moreover, the addition of the dispersion correction for BLYP yields an oxygen-oxygen radial distribution function in excellent agreement with experiment. Thus, we conclude that one can obtain a very satisfactory model for water using BLYP and a correction for dispersion.

We present a detailed calculation of partial charges for the 1,3-dimethylimidazolium chloride ionic liquid. We first analyze MP2 electronic structure calculations and DFT results on isolated ion pairs with various methods of assigning partial charges to the atomic centers. In a second run we analyze the trajectory of a 25 ps long Car-Parrinello MD run of 30 ion pairs under bulk conditions using a charge fitting procedure due to Blöchl. Both, the single ion pair and the bulk system, provide us with a similar total ionic charge considerably less than unity. Especially the liquid state DFT results give convincing evidence for a reduced ionic charge on the ions. The similarity of both results suggest that the delocalization of the Cl charge is due only to local interactions. The relevance of our results is 2-fold; on the one hand they shed light on the basic property of the liquid and its reduced ionic character, and on the other hand, the ab initio derived partial charges provide a fundamental theoretical basis for the recent attempts to use the total ionic charge as an adjustable parameter. Furthermore, all our partial charges are subject to large fluctuations, hinting to the importance of polarization effects.