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Like-Charge Attraction at the Nanoscale: Ground-State Correlations and Water Destructuring
Ivan Palaia1, Abhay Goyal2, Emanuela Del Gado2
1Institute of Science and Technology Austria, 3400 Klosterneuburg, Austria.
The Journal of Physical Chemistry. B
|April 14, 2022
Summary
Ionic correlations drive like-charge attraction, challenging electrostatics. This study reveals ground-state physics governs interactions in confined systems, explaining exotic attraction in materials like cement and clays.
Area of Science:
- Soft and hard matter physics
- Electrostatics
- Colloid and surface science
Background:
- Like-charge attraction, driven by ionic correlations, contradicts classical electrostatic theories.
- Understanding these forces is crucial for soft and hard matter systems.
Purpose of the Study:
- To investigate the fundamental physics governing interactions between like-charged surfaces confined with counterions and water.
- To develop a predictive model for interaction pressure in such systems.
- To explain the observed attractive forces in materials like cement and clays.
Main Methods:
- Theoretical derivation of interaction pressure based on ground-state physics.
- Validation against implicit-solvent Monte Carlo simulations.
- Testing against explicit-solvent simulations of cement and various clays.
Main Results:
- The relevant physics is ground-state dominated, irrespective of fluctuations.
- A simple, accurate interaction pressure equation was derived and validated.
- Reduced dielectric screening due to water destructuring under confinement enhances ionic correlations.
Conclusions:
- The derived equation of state explains the exotic attractive regime in materials like cement and clays.
- This phenomenon occurs even without multivalent counterions, driven by enhanced ionic correlations.
- The findings challenge conventional electrostatic understanding in confined systems.
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