Ion-Specific and pH-Dependent Hydration of Mica–Electrolyte Interfaces

High Resolution Image Download MS PowerPoint Slide Hydration forces play a crucial role in a wide range of phenomena in physics, chemistry, and biology. Here, we study the hydration of mica surfaces in contact with various alkali chloride solutions over a wide range of concentrations and pH values. Using atomic force microscopy and molecular dynamics simulations, we demonstrate that hydration forces consist of a superposition of a monotonically decaying and an oscillatory part, each with a unique dependence on the specific type of cation. The monotonic hydration force gradually decreases in strength with decreasing bulk hydration energy, leading to a transition from an overall repulsive (Li +, Na + ) to an attractive (Rb +, Cs + ) force. The oscillatory part, in contrast, displays a binary character, being hardly affected by the presence of strongly hydrated cations (Li +, Na + ), but it becomes completely suppressed in the presence of weakly hydrated cations (Rb +, Cs + ), in agreement with a less pronounced water structure in simulations. For both aspects, K + plays an intermediate role, and decreasing pH follows the trend of increasing Rb + and Cs + concentrations.