A transferable ab initio based force field for aqueous ions

Sami Tazi (1) , John J. Molina (1) , Benjamin Rotenberg (1) , Pierre Turq (1) , Rodolphe Vuilleumier (2) , Mathieu Salanne (1) , John Molina (1)

1 PECSA - Physicochimie des Electrolytes, Colloïdes et Sciences Analytiques
2 Département de Chimie - ENS Paris

We present a new polarizable force field for aqueous ions (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+ and Cl-) derived from condensed phase ab-initio calculations. We use Maximally Localized Wannier Functions together with a generalized force and dipole-matching procedure to determine the whole set of parameters. Experimental data is then used only for validation purposes and a good agreement is obtained for structural, dynamic and thermodynamic properties. The same procedure applied to crystalline phases allows to parametrize the interaction between cations and the chloride anion. Finally, we illustrate the good transferability of the force field to other thermodynamic conditions by investigating concentrated solutions.

Domaines: Chimie-Physique [physics.chem-ph]; Mécanique statistique [cond-mat.stat-mech]

Sami Tazi, John J. Molina, Benjamin Rotenberg, Pierre Turq, Rodolphe Vuilleumier, et al.. A transferable ab initio based force field for aqueous ions. Journal of Chemical Physics, 2012, 136 (11), pp.114507. ⟨10.1063/1.3692965⟩. ⟨hal-01897599⟩