title: Hydration of sodium, potassium, and chloride ions in solution and the concept of structure maker/breaker.
abstract: Neutron diffraction data with hydrogen isotope substitution on aqueous solutions of NaCl and KCl at concentrations ranging from high dilution to near-saturation are analyzed using the Empirical Potential Structure Refinement technique. Information on both the ion hydration shells and the microscopic structure of the solvent is extracted. Apart from obvious effects due to the different radii of the three ions investigated, it is found that water molecules in the hydration shell of K+ are orientationally more disordered than those hydrating a Na+ ion and are inclined to orient their dipole moments tangentially to the hydration sphere. Cl- ions form instead hydrogen-bonded bridges with water molecules and are readily accommodated into the H-bond network of water. The results are used to show that concepts such as structure maker/breaker, largely based on thermodynamic data, are not helpful in understanding how these ions interact with water at the molecular level.
authors.affiliation: Dipartimento di Fisica E. Amaldi, Università degli Studi Roma Tre, Via della Vasca Navale 84, 00146 Roma, Italy.
authors.forename: R
authors.initials: R
authors.lastname: Mancinelli
authors.forename: A
authors.initials: A
authors.lastname: Botti
authors.forename: F
authors.initials: F
authors.lastname: Bruni
authors.forename: M A
authors.initials: MA
authors.lastname: Ricci
authors.forename: A K
authors.initials: AK
authors.lastname: Soper