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Phys Rev E Stat Nonlin Soft Matter Phys. 2012 Sep;86(3):031504. doi: 10.1103/PhysRevE.86.031504. Epub 2012 Sep 17.

Spatial inhomogeneities in ionic liquids, charged proteins, and charge stabilized colloids from collective variables theory.

Physical review. E, Statistical, nonlinear, and soft matter physics

O Patsahan, A Ciach

Affiliations

  1. Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine, 1 Svientsitskii Str., 79011 Lviv, Ukraine.

PMID: 23030920 DOI: 10.1103/PhysRevE.86.031504

Abstract

Effects of size and charge asymmetry between oppositely charged ions or particles on spatial inhomogeneities are studied for a large range of charge and size ratios. We perform a stability analysis of the primitive model of ionic systems with respect to periodic ordering using the collective variables-based theory. We extend previous studies [Ciach et al., Phys. Rev. E 75, 051505 (2007)] in several ways. First, we employ a nonlocal approximation for the reference hard-sphere fluid which leads to the Percus-Yevick pair direct correlation functions for the uniform case. Second, we use the Weeks-Chandler-Anderson regularization scheme for the Coulomb potential inside the hard core. We determine the relevant order parameter connected with the periodic ordering and analyze the character of the dominant fluctuations along the λ lines. We show that the above-mentioned modifications produce large quantitative and partly qualitative changes in the phase diagrams obtained previously. We discuss possible scenarios of the periodic ordering for the whole range of size and charge ratios of the two ionic species, covering electrolytes, ionic liquids, charged globular proteins or nanoparticles in aqueous solutions, and charge-stabilized colloids.

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