Real-time observation of the destruction of hydration shells under electrochemical force

Major alteration or even destruction of the hydration shell around interacting molecules and ions in solution is an important process that determines how hydrated substances interact. Therefore, the direct observation of structural changes in hydration shells around solutes in close contact with other solutes or surfaces is important for understanding chemical processes that take place in solution. In the work described in this paper, time-resolved IR absorption measurements were performed to study the interaction of hydrated Na(+) or tetrapropylammonium cation (Pr4N(+)) with a hydrophobic CO-covered Pt surface; the adsorption force between cations and the surface was controlled by using an electrochemical system. We found that the hydrophobic hydration shell of Pr4N(+) is initially stabilized on the hydrophobic surface, but application of a strong force to the cation approaching CO destroys the water layers between them. This process is rather slow, taking a few hundred milliseconds. Hydrophilic Na(+) behaves quite differently from Pr4N(+) due to the different structure of its hydration shell. These experimental results are supported by molecular dynamics simulations.