A molecular dynamics study on Rh3+ hydration: development and application of a first principles hydrated ion–water interaction potential

Abstract

The Rh3+ aquaion exhibits one of the largest residence times of water molecules in the first hydration shell. The extreme stability of this hexahydrated ion in water solutions makes Rh3+ an extremely suitable candidate to be studied using the hydrated ion model. According to this approach, the representative cationic entity in aqueous solution is the ion plus its first hydration shell (i.e. the hydrated ion) and not the bare ion. Our group has successfully applied that concept in the framework of classical statistical simulations based on first principles ion–water interaction potentials. The methodology is now applied to the [Rh(H2O)6]3+ case based on a previous generalization in which some of the contributions were found to be transferable among the cases already studied (Cr3+, Al3+, Mg2+, Be2+). In this contribution a flexible hydrate model is presented, in which rigid first-shell water molecules have rotational and translational degrees of freedom, allowing for internal dynamics of the hydrated ion entity. The potential presented is thoroughly tested by means of a set of molecular dynamics simulations. Structural, dynamical, energetic and spectroscopic information is retrieved from the simulations, allowing the estimation of properties such as ion hydration energy, vibrational spectra of the intermolecular modes, cation mobility, rotational dynamics of the hydrated ion and first-shell water molecules and residence times of the second-shell water molecules. Extension of the Ewald sum to terms r−4, r−6 and r−7 is presented and applied to systems of different size ([Rh(H2O)6]3++(n−6)H2O, n=50, 100, 200, 500, 1000 and 2500) and cutoff radii.