Reversible state transition in nanoconfined aqueous solutions

Phys Rev Lett. 2014 Feb 21;112(7):078301. doi: 10.1103/PhysRevLett.112.078301. Epub 2014 Feb 20.

Abstract

Using molecular dynamics simulations, we find a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, which is not observed in macroscopic systems. The nanoscale confinement also leads to a significant increase of the critical aggregation concentration (CAC). A theoretical model based on Gibbs free energy calculation is developed to describe the simulation results. It indicates that the reversible state transition is attributed to the low free energy barrier (of order kBT) in between two energy minima corresponding to the dispersion and aggregation states, and the enhancement of the CAC results from the fact that at lower concentrations the number of solute molecules is not large enough to allow the formation of a stable cluster in the confined systems.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Models, Chemical*
  • Molecular Dynamics Simulation
  • Nanoparticles / chemistry*
  • Phase Transition
  • Solutions / chemistry
  • Thermodynamics
  • Water / chemistry*

Substances

  • Solutions
  • Water