Ions in solutions: Determining their polarizabilities from first-principles

J.J. Molina (1, 2, 3) , S. Lectez (4) , S. Tazi (1, 2, 3) , M. Salanne (1, 2) , Jean-François Dufrêche (3) , J. Roques (4) , E. Simoni (4) , P. A. Madden , P. Turq (1, 2, 3)

1 PECSA - Physicochimie des Electrolytes, Colloïdes et Sciences Analytiques
2 UPMC - Université Pierre et Marie Curie - Paris 6
3 LMCT - Modélisation Mésoscopique et Chimie Théorique
4 IPNO - Institut de Physique Nucléaire d'Orsay

Dipole polarizabilities of a series of ions in aqueous solutions are computed from first-principles. The procedure is based on the study of the linear response of the maximally localized Wannier functions to an applied external field, within density functional theory. For most monoatomic cations (Li+, Na+, K+, Rb+, Mg2+, Ca2+ and Sr2+) the computed polarizabilities are the same as in the gas phase. For Cs+ and a series of anions (F−, Cl−, Br− and I−), environmental effects are observed, which reduce the polarizabilities in aqueous solutions with respect to their gas phase values. The polarizabilities of H( aq )+, OH( aq )− have also been determined along an ab initio molecular dynamics simulation. We observe that the polarizability of a molecule instantaneously switches upon proton transfer events. Finally, we also computed the polarizability tensor in the case of a strongly anisotropic molecular ion, UO22+. The results of these calculations will be useful in building interaction potentials that include polarization effects.

Domaines: Chimie-Physique [physics.chem-ph]

J.J. Molina, S. Lectez, S. Tazi, M. Salanne, Jean-François Dufrêche, et al.. Ions in solutions: Determining their polarizabilities from first-principles. Journal of Chemical Physics, 2011, 134, pp.014511. ⟨10.1063/1.3518101⟩. ⟨in2p3-00575117⟩