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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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Superionic Colloidal Crystals: Ionic to Metallic Bonding Transitions.

Yange Lin1, Monica Olvera de la Cruz1,2,3

  • 1Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.

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|August 26, 2022
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Summary
This summary is machine-generated.

We discovered an ionic to metallic bonding transition in charged colloidal crystals. This transition occurs when small particles melt into the larger crystal lattice, driven by increased temperature or particle concentration.

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Area of Science:

  • Colloid Science
  • Materials Science
  • Statistical Mechanics

Background:

  • Size-asymmetric binary charged colloidal solutions self-assemble into ionic colloidal crystals.
  • These crystals are typically stabilized by ionic-type bonding, with smaller particles fixed within the larger lattice.
  • A transition to metallic bonding, where the smaller component lattice melts while the larger remains intact, is investigated.

Purpose of the Study:

  • To investigate the ionic to metallic bonding transition in charged colloidal systems.
  • To understand the factors driving this transition, such as temperature and particle concentration.
  • To analyze the thermodynamic driving forces behind the observed transition.

Main Methods:

  • Simulations of a charged colloidal crystal in equilibrium with a solution of small particles and counterions.
  • Utilizing Coulomb interactions between finite-size components.
  • Free energy calculations using Madelung constant and Wigner-Seitz cell approaches combined with the quasi-harmonic lattice model.

Main Results:

  • First-order ionic to metallic transitions were observed upon increasing temperature or small particle concentration.
  • The transition involved lattice expansion and increased incorporation of small particles into the crystal.
  • Simulations and calculations reproduced the transition, indicating a more pronounced enthalpic than entropic gain.

Conclusions:

  • Charged colloidal crystals can undergo a reversible ionic to metallic bonding transition.
  • Temperature and solution composition are key parameters controlling this transition.
  • The transition is thermodynamically driven by enthalpic contributions during material exchange with the solution.