title: Ions in solutions: Determining their polarizabilities from first-principles.
abstract: 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(+), Mg(2+), Ca(2+) and Sr(2+)) 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, UO(2) (2+). The results of these calculations will be useful in building interaction potentials that include polarization effects.
authors.affiliation: UPMC Univ Paris 06, UMR 7195, PECSA, F-75005, Paris, France.
authors.forename: John J
authors.initials: JJ
authors.lastname: Molina
authors.forename: Sébastien
authors.initials: S
authors.lastname: Lectez
authors.forename: Sami
authors.initials: S
authors.lastname: Tazi
authors.forename: Mathieu
authors.initials: M
authors.lastname: Salanne
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Dufrêche
authors.forename: Jérôme
authors.initials: J
authors.lastname: Roques
authors.forename: Eric
authors.initials: E
authors.lastname: Simoni
authors.forename: Paul A
authors.initials: PA
authors.lastname: Madden
authors.forename: Pierre
authors.initials: P
authors.lastname: Turq
mesh_terms: D007477:Ions / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D012996:Solutions; D014867:Water / Q000737:chemistry
chemical_list: D007477:Ions; D012996:Solutions; D014867:Water