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Ionic size effects on the Poisson-Boltzmann theory.

Thiago Colla¹, Lucas Nunes Lopes², Alexandre P Dos Santos²

¹Instituto de Física, Universidade Federal de Ouro Preto, CEP 35400-000 Ouro Preto, MG, Brazil.

The Journal of Chemical Physics

|July 10, 2017

Summary

This study presents a simple theory accounting for ion size effects on ionic distributions around charged particles. The model shows excellent agreement with simulations, improving predictions for colloids in electrolyte solutions.

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Area of Science:

Physical Chemistry
Colloid Science
Computational Chemistry

Background:

Understanding ionic distributions around charged particles is crucial in colloid and surface chemistry.
Traditional Poisson-Boltzmann theory often neglects finite ion size effects.
Accurate modeling is needed for applications involving nanoparticles and electrolytes.

Purpose of the Study:

To develop a simple theory incorporating ionic size effects into ionic distributions around charged spherical particles.
To provide a more accurate mean-field description beyond the classical Poisson-Boltzmann equation.
To validate the new theory against advanced simulation methods.

Main Methods:

Developed a modified Poisson-Boltzmann equation including a correction for finite ion size.
Employed Monte Carlo simulations for comparison.
Utilized density functional theory with fundamental measure approach and second-order bulk expansion.

Main Results:

The developed theory accurately predicts ionic distributions around charged spherical particles, even for multivalent ions.
Excellent agreement was observed between the theory and Monte Carlo simulations.
The theory effectively accounts for electrostatic correlations and ion size.

Conclusions:

The simple theory provides a highly accurate description of ion distributions around charged particles, considering ion size.
This approach is particularly effective for ions with large effective radii at low concentrations.
The findings are applicable to electrolytes interacting with colloids and nanoparticles.