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NaCl crystallization in apolar nanometer-sized confinement studied by atomistic simulations.

Immanuel Kalcher1, Joachim Dzubiella2

  • 1Physics Department, Technical University Munich, 85748 Garching, Germany.

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|February 4, 2014
PubMed
Summary

Molecular dynamics simulations reveal that NaCl crystallization is suppressed in narrow apolar confinements due to ion expulsion. Stable crystals form only in wider confinements (above 2 nm) with specific orientations.

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Area of Science:

  • Materials Science
  • Physical Chemistry
  • Nanotechnology

Background:

  • Understanding salt crystallization is crucial for applications like supercapacitors and geological processes.
  • The behavior of salt in confined environments, particularly apolar ones, is not well understood at the molecular level.

Purpose of the Study:

  • To investigate the structure and growth of sodium chloride (NaCl) crystals in bulk versus nanometer-sized apolar confinement.
  • To elucidate the molecular mechanisms governing NaCl crystallization under confinement.

Main Methods:

  • Explicit-water molecular dynamics computer simulations were employed.
  • Simulations were conducted in both bulk and pseudo grand canonical/canonical setups for confinement studies.
  • Analysis focused on ion concentration, crystallization, and crystal orientation within different confinement widths.

Main Results:

  • In bulk, NaCl crystallization is rapid above a supersaturation threshold.
  • In narrow apolar confinement (<1.5 nm), NaCl is expelled, leading to low internal ion concentration and suppressed crystallization.
  • Stable NaCl crystals form in wider apolar confinements (>2 nm) with the (100) plane parallel to the surface, featuring a hydration layer.

Conclusions:

  • Apolar nanoconfinement significantly alters NaCl crystallization behavior, primarily through ion expulsion.
  • Capillary evaporation of ions occurs in very narrow confinements.
  • Findings have implications for double-layer supercapacitors and geological salt weathering.