Water-mediated ion-ion interactions are enhanced at the water vapor-liquid interface

There is overwhelming evidence that ions are present near the vapor–liquid interface of aqueous salt solutions. Charged groups can also be driven to interfaces by attaching them to hydrophobic moieties. Despite their importance in many self-assembly phenom- ena, how ion–ion interactions are affected by interfaces is not understood. We use molecular simulations to show that the effec- tive forces between small ions change character dramatically near the water vapor–liquid interface. Specifically, the water-mediated attraction between oppositely charged ions is enhanced relative to that in bulk water. Further, the repulsion between like-charged ions is weaker than that expected from a continuum dielectric description and can even become attractive as the ions are drawn to the vapor side. We show that thermodynamics of ion associa- tion are governed by a delicate balance of ion hydration, in- terfacial tension, and restriction of capillary fluctuations at the interface, leading to nonintuitive phenomena, such as water- mediated like charge attraction. “Sticky” electrostatic interactions may have important consequences on biomolecular structure, as- sembly, and aggregation at soft liquid interfaces. We demonstrate this by studying an interfacially active model peptide that changes its structure from α-helical to a hairpin-turn–like one in response to charging of its ends.

@article{venkateshwaran2014water,
  title   = {Water-mediated ion-ion interactions are enhanced at the water vapor-liquid interface},
  author  = {Venkateshwaran, Vasudevan and Vembanur, Srivathsan and Garde, Shekhar},
  journal = {Proc. Natl. Acad. Sci. USA},
  volume  = {111},
  number  = {24},
  pages   = {8729-8734},
  year    = {2014},
  doi     = {10.1073/pnas.1403294111}
}