AVS2013 Session IA+AI+BI+IS+NL+SS-MoA: Ions at Aqueous Interfaces

Ions at water interfaces can significantly change the chemical and physical properties, and hence the functionality, of the interfaces. They play a key role in many important processes in many disciplines. In recent years, sum-frequency vibrational spectroscopy(SFVS) has been demonstrated to be a unique, effective tool to study such interfaces. We discuss here SFVS investigations of ions at various water interfaces: soluble ions at air/water interfaces, ions attached to Langmuir monolayers on water, and hydrophilic and hydrophobic water interfaces. Formation of an electric double charge layer by ions near an interface usually occurs. It induces significant polar reorientation of interfacial water molecules and alters their vibrational spectra that can be detected by SFVS. Useful structural information can be deduced from the results, but work is still needed for complete understanding of the results.

We investigate the vibrational dynamics and energy transfer between interfacial water molecules, in the presence of sodium chloride and sodium iodide salts, using 2-dimensional, femtosecond surface-specific vibrational spectroscopy. We find that both the vibrational lifetime and the intramolecular energy transfer for anion associated interfacial water molecules is slower than for non ion-bound interfacial water molecules. The analysis of the time-dependent slope of the 2-dimensional sum frequency response reveals that the intermolecular resonant energy transfer between the interfacial water molecules is significantly slowed down by the presence of ions. Accordingly, the decay of the frequency-frequency correlation function is slower for NaI than for NaCl solution. This finding provides direct evidence of the higher surface propensity for iodide than for chloride ion, and allows for the quantification of interfacial density of halide ions for both systems.

Vibrational Sum Frequency Spectroscopy (VSFS) has been used to systematically study the preferential adsorption of a series of monovalent ions to charged and uncharged fatty acid monolayers. Ion enrichment is mainly determined indirectly by targeting surface water vibrational modes. In selected cases however, the ion presence is also directly determined by targeting the fatty acid carboxylate headgroups. A major effort is made to understand the effect of co-ions in the molecular properties of these biophysically relevant interfaces.

The molecular layer of water molecules on surfaces, the so-called hydration layer, is important for a whole number of properties of biological as well as technological surfaces. Insight can be gained from all-atomistic simulations in conjunction with appropriate continuum modeling.

- Dielectric properties of interfacial water layers are important for the design of high-power capacitors, and can be resolved using simulations.

- At the same time, ions accumulate into a highly condensed interfacial layer, leading to the well-known saturation of the electro-osmotic mobility at large surface charge density regardless of the hydrodynamic boundary conditions. The experimentally well-established apparent excess surface conductivity follows for all hydrodynamic boundary conditions without additional assumptions.

- Hydration water at biological membranes absorbs electromagnetic radiation specifically in the 0.1-10 GHz range that is used for radio communication. Possible health issues are discussed.

Acetonitrile in water is known to exhibit non-ideal behavior. At low concentrations, acetonitrile molecules migrate towards the solution interface leaving water mostly in the bulk. At 0.2 mole fraction, the surface saturates with a full monolayer. Above 0.2 mf, the acetonitrile signal at the surface is enhanced relative to that of the bulk with increasing solution concentration. In the bulk, acetonitrile and water form clusters between 0.2 and 0.7 mole fraction and interact with each other through dipole interactions. Propionitrile, another nitrile with a lower solubility, is also shown have a propensity for the surface of aqueous solutions.

Ions have been shown to impact the properties and solvation structure of aqueous solutions, both at the surface and in the bulk of solution. Potassium iodide (KI) was added to acetonitrile and propionitrile aqueous solutions to observe the effects of ions on nitrile distributions. Liquid jet-X-ray photoelectron spectroscopy (LJ-XPS) was used to characterize the elemental compositions of ions and nitrile species. By tuning the incident photon energy, different depths of the solutions is observed; at low kinetic energies the solution surface is probed and the high kinetic energies the bulk of solution is probed. After adding KI, the interfacial photoelectron spectroscopy signal reveals a reduction in nitrogen and carbon signals in acetonitrile, demonstrating the salting-in effect. With addition of ions to aqueous propionitrile solutions, nitrogen and carbon signals are increased, suggesting a salting-out effect. Sodium chloride ions are also added to aqueous propionitrile studies to determine differences between ions effects from the KI and NaCl salts on propionitrile solutions. These studies help elucidate the role ions play at the interface of aqueous organic solutions.

The understanding of the surface interaction in electrolyte solutions is of paramount importance in many fields such us biology, electrochemistry and surface chemistry. Aqueous solutions of high concentrations are mainly interesting from practical point of view (batteries). In principle, AFM through the Force versus Distance curves (F-D) can be successfully used to probe the electrolyte layering at solid-liquid interfaces and investigate the nature of hydration forces in the presence of various electrolytes of different ion valency, ion concentration or pH [1].

In the current work AFM has been used to measure hydration forces between a non-coated Silicon colloid probe and atomically smooth, flat freshly cleaved Mica surfaces, in highly concentrated monovalent electrolytes (LiCl, NaCl, CsCl). The effect of i) the cation hydration diameter (Li⁺>Na⁺>Cs⁺) and ii) the electrolyte’s concentration (0.05-3.0 M), on both the structural (F_STR) and adhesion (F_ADH) forces are studied. In all environments, F_ADH values pass through a minimum as a function of electrolyte’s concentration, while for each salt solution, the frequency of structural events is calculated as a function of its concentration. The number of the F-D curves, were classified in appropriate tables according to the number of the structural hydration layers observed. Furthermore, depending on the concentration, 1, 2 or even up to 5 consecutive hydration layers can be clearly distinguished in the same F-D curve from which both the force and the range of each layer can be measured. These results are compared with the hydrated radii of the above ions enabling the extrusion of useful statements concerning the re-arrangement of the structured cation/water layer at the liquid/solid interface.