Publications

Theoretical study of aqueous solvation of K+ comparing ab initio, polarizable, and fixed-charge models

Whitfield, Troy W.; Varma, Sameer V.; Harder, Edward; Lamoureux, Guillaume; Rempe, Susan B.; Roux, Benoit

The hydration of K+ is studied using a hierarchy of theoretical approaches, including ab initio Born-Oppenheimer molecular dynamics and Car-Parrinello molecular dynamics, a polarizable force field model based on classical Drude oscillators, and a nonpolarizable fixed-charge potential based on the TIP3P water model. While models based more directly on quantum mechanics offer the possibility to account for complex electronic effects, polarizable and fixed-charges force fields allow for simulations of large systems and the calculation of thermodynamic observables with relatively modest computational expense. A particular emphasis is placed on investigating the sensitivity of the polarizable model to reproduce key aspects of aqueous K+, such as the coordination structure, the bulk hydration free energy, and the self-diffusion of K+. It is generally found that, while the simple functional form of the polarizable Drude model imposes some restrictions on the range of properties that can simultaneously be fitted, the resulting hydration structure for aqueous K+ agrees well with experiment and with more sophisticated computational models. All the computational models yield a similar hydration structure, with a first peak in the radial distribution function near 2.7 Å, though the distribution functions obtained from the two ab initio simulations are less sharply peaked. A counterintuitive result, seen in Car-Parrinello molecular dynamics and in simulations with the Drude polarizable force field, is that the average induced molecular dipole of the water molecules within the first hydration shell around K+ is slightly smaller than the corresponding value in the bulk. In final analysis, the perspective of K+ hydration emerging from the various computational models is broadly consistent with experimental data, though at a finer level there remain a number of issues that should be resolved to further our ability in modeling ion hydration accurately. © 2007 American Chemical Society.