This study systematically examines the interactions of the hexafluorophosphate anion (PF6-) with one or two solvent water molecules (PF6-(H2O)n where n = 1, 2). Full geometry optimizations and subsequent harmonic vibrational frequency computations are performed on each stationary point using a variety of common density functional theory methods (B3LYP, B3LYP-D3, M06-2X, and ωB97XD) and the MP2 and CCSD(T) ab initio methods with a triple-ζ correlation consistent basis set augmented with diffuse functions on all non-hydrogen atoms (cc-pVTZ for H and aug-cc-pVTZ for P, O, and F; denoted as haTZ). Five new stationary points of PF6-(H2O)2 have been identified, one of which has an electronic energy of approximately 2 kcal mol-1 lower than the only other dihydrate structure reported for this system. The CCSD(T) computations also reveal that the detailed interactions between PF6- and H2O can be quite difficult to model reliably, with some methods struggling to correctly characterize stationary points for n = 1 or accurately reproduce the vibrational frequency shifts induced by the formation of the hydrated complex. Although the interactions between the solvent and ionic solute are quite strong (CCSD(T) electronic dissociation energy ≈10 kcal mol-1 for the monohydrate minimum), the solvent-solvent interactions in the lowest-energy PF6-(H2O)2 minimum give rise to appreciable cooperative effects not observed in the other dihydrate minima. In addition, this newly identified structure exhibits the largest frequency shifts in the OH stretching vibrations for the waters of hydration (with Δω exceeding -100 cm-1 relative to the values for an isolated H2O molecule).